KR101967408B1 - Photocurable Resin Composition, Method for Preparing the Same and Optical Film Comprising the Same - Google Patents

Abstract

The present invention relates to a photocurable resin composition, a method for manufacturing the same, and an optical film including the same. More specifically, the photocurable resin composition includes an organophosphate-based (meth) acrylate and a phenol compound to secure storage stability, thereby being suitable as a material for transparent displays.

Description

Photocurable resin composition, preparation method thereof, and optical film comprising same {Photocurable Resin Composition, Method for Preparing the Same and Optical Film Comprising the Same}

The present invention relates to a photocurable resin composition having enhanced stability, a method for preparing the same, and an optical film including the same.

Quantum dots are nanoparticles having a size of several tens of nanometers or less having semiconductor characteristics, and have different characteristics from bulk particles due to quantum limiting effects. Specifically, the bandgap may vary according to the size of the quantum dots, and thus the wavelength of absorption may be changed, and the quantum limiting effect due to the small size shows new optical, electrical, and physical properties not found in bulk materials. Therefore, research into a technique for manufacturing a photoelectric conversion element such as a solar cell (solar cell) and a light emitting diode using such a quantum dot has been actively conducted.

However, since quantum dots are vulnerable to moisture and oxygen in themselves and have poor stability, attempts to compensate for such problems are continued in the field of quantum dot film production using quantum dots as a raw material.

The quantum dot film can be produced by a process of laminating a first substrate and a second substrate (hereinafter, a barrier layer) through ultraviolet curing using a polymer matrix in which quantum dot particles are dispersed. Since the barrier layer is characterized in that the metal oxide coating to prevent moisture penetration, most of the quantum dot film is prepared using a photocurable compound having a hydrogen bond functional group having excellent adhesion to the metal oxide.

However, such a film can secure adhesion to the barrier layer, but exhibits vulnerability to moisture and oxygen, thereby deteriorating reliability of the quantum dot film. In order to make up for this drawback, a method of using curing of a thiol alkene compound system has been proposed. In the case of the thiol alkene compound system, photoinitiator initiates radical reaction by UV light, the alkene resin is polymerized, radicals and thiols generated in the alkene resin are used as another curing mechanism through the chain transfer reaction and the Michael reaction of thiol and olefin. By implementing the IPN (Interpenetrating polymer network) structure to be cured significantly shrinkage of the curing shrinkage and combination of the thiol and the metal oxide, it is possible to secure the adhesion between the barrier layers.

In addition, thiol has a hydrogen bonding property, but has a hydrophobic property to prevent penetration into moisture and oxygen. Despite these advantages, thiol and alkene compounds have a problem of storage stability that thickens or gels upon mixing. Regardless of the presence or absence of all initiators, the thiol-ene reaction proceeds as a spontaneous dark reaction (Dark Reaction), and especially when the reaction proceeds by heat or light and is not immediately mixed and used, there are many restrictions on mass production.

Japanese Patent Laid-Open No. 2004-035734 refers to an active energy containing an N-nitroso compound in a thio-ene composition. In particular, the N-nitroso compound uses compounds such as aluminum N-nitrosophenylhydroxylamine and N-nitrosophenylhydroxylamine, but the compound is extremely limited in use as a carcinogenic substance, the composition is at room temperature Stability is improved, but it is not perfect and is less effective at high temperatures.

Japanese Patent No. 54753333 describes 4-methoxy-1-naphthol as a thiol compound, an ethylenically unsaturated double bond-containing compound having two or more unsaturated double bond groups, and a naphthalene compound containing a hydroxyl group and an alkyl (alkoxy) group. have. However, the 4-methoxy-1-naphthol has a secondary thiol effect such as pentaerythritol tetrakis (3-mercapto butylate), which is relatively poor in reactivity with a double bond, and is ineffective for primary thiol. In addition, it has little effect at high temperatures and lacks color for use as an optical material.

Korean Patent Application Publication No. 2018-0075653 discloses a compound having a pKa value of 5.0 or less as a reaction inhibitor, a compound containing a benzene ring and / or a naphthalene ring containing a hydroxyl group as a radical inhibitor, and water to impart stability to a thio-ene composition. Is starting. However, acid compounds having a pKa value of 5 or less have a problem of compatibility with thiol compounds, and it is difficult to obtain a transparent cured product, and thus there is a problem in the application of an optical material that must be accompanied by transparency. It is difficult to apply to the resulting display material.

As such, researches to supplement the stability of the quantum dots are actively conducted, but the problems that are vulnerable to moisture and oxygen have not been completely improved, and thus technology development to secure the stability of the quantum dots needs to be made.

Japanese Laid-Open Patent No. 2004-035734 Japanese Patent No.5647533 Korean Patent Publication No. 2018-0075653

The present inventors conducted various studies to solve the above problems, and as a result, a photocurable resin composition was prepared using an organophosphite (meth) acrylate compound and a phenol compound, and the photocurable resin composition was excellent. It has a storage stability to ensure a long available time.

Accordingly, it is an object of the present invention to provide a photocurable resin composition having enhanced stability and a method for producing the same.

In order to achieve the said objective, this invention is a (meth) acrylate compound (A); Thiol compound (B) comprising two or more mercapto groups in one molecule; And photoinitiators (C); As a photocurable resin composition comprising:

Organophosphate-based (meth) acrylates represented by Formula 1; And a phenolic compound represented by Formula 2 or Formula 3 below: Photocurable resin composition comprising:

<Formula 1>

R ₁ in Formula 1 is selected from Formula 1-1, Formula 1-2, Formula 1-3, and Formula 1-4, R ₂ is hydrogen or methyl, and n is an integer of 1 to 3:

<Formula 1-1>

<Formula 1-2>

<Formula 1-3>

<Formula 1-4>

X in Formulas 1-1 to 1-4 may be the same as or different from each other, and is an integer of 0 to 10; And

<Formula 2>

<Formula 3>

In Formula 2 or Formula 3, R ₃ to R ₉ may be each independently the same or different, hydrogen, -OH, -COOH, C ₁ to C ₁₀ linear or pulverized alkyl, C ₁ to C ₁₀ straight chain Or pulverized alkoxy alkyl, C ₁ to C ₁₀ linear or pulverized alkyl containing ester groups.

The present invention also provides a (S1) (meth) acrylate compound (A); Thiol compound (B) comprising two or more mercapto groups in one molecule; And photoinitiators (C); Organophosphate (Organophosphate) -based (meth) acrylate represented by Formula 1; And it provides a method for producing a photocurable resin composition comprising the step of removing moisture from the mixture of; a phenolic compound represented by the formula (2) or (3).

This invention also provides the optical film containing the said photocurable resin composition.

The photocurable resin composition according to the present invention exhibits stable characteristics regardless of temperature, that is, low temperature and room temperature, as well as high temperature, and thus has excellent storage stability, thereby ensuring a long pot life.

The photocurable resin composition exhibiting such stable characteristics simultaneously contains an organophosphite compound and a phenolic compound. The photocurable resin composition does not have a large change in viscosity, and thus is excellent in storage stability and excellent in high temperature and high humidity.

In addition, the optical film made of the photocurable resin composition is excellent in the adhesive strength of the angle contained therein, excellent brightness even at high temperature and high humidity, there is little change in color even in the harsh environment is suitable as a material for transparent display .

1 is an H-NMR and FT-IR graph of an organophosphite compound obtained in Synthesis Example 1. FIG.
2 is a 1H-NMR and FT-IR graph of an organophosphite compound obtained in Synthesis Example 2. FIG.
3 is an H-NMR and FT-IR graph of the organophosphite compound obtained in Synthesis Example 3. FIG.

Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.

The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best describe their invention. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

Photocurable  Resin composition

The present invention mixes an organophosphite-based (meth) acrylate and a phenolic compound, which can act as a radical polymerization inhibitor, to a thio-ene composition comprising a thiol compound and an alkene compound, which are conventionally used as a photocurable resin composition. The present invention relates to a photocurable resin composition having enhanced stability. At this time, the thiol compound means a compound containing a mercapto group or a thiol group, the alkene compound means a compound containing an ethylenic carbon-carbon double bond.

For example, the "thio-ene composition" in the present invention is a (meth) acrylate compound (A); A thiol compound (B) comprising two or more mercapto groups in one molecule; means a mixture comprising.

The present invention provides a (meth) acrylate compound (A); Thiol compound (B) comprising two or more mercapto groups in one molecule; And photoinitiators (C); A photocurable resin composition comprising: an organophosphate-based (meth) acrylate represented by Formula 1 below; And a phenolic compound represented by Formula 2 or 3 below, and further relates to a photocurable resin composition which may further include at least one of quantum dot particles (D) and scattering particles (E):

<Formula 1>

In Formula 1, R ₁ may be selected from Formula 1-1, Formula 1-2, Formula 1-3, and Formula 1-4, R ₂ is hydrogen or methyl, and n is an integer of 1 to 3:

<Formula 1-1>

<Formula 1-2>

<Formula 1-3>

<Formula 1-4>

X in Formulas 1-1 to 1-4 may be the same as or different from each other, and is an integer of 0 to 10; And

<Formula 2>

<Formula 3>

In Formula 2 or Formula 3, R ₃ to R ₉ may be each independently the same or different, hydrogen, -OH, -COOH, C ₁ to C ₁₀ linear or pulverized alkyl, C ₁ to C ₁₀ straight chain Or pulverized alkoxy alkyl, C ₁ to C ₁₀ linear or pulverized alkyl containing ester groups.

In the present invention, the organophosphite-based (meth) acrylate represented by Formula 1 may be defined as phosphoric acid to which a (meth) acryl group is introduced. The organophosphite-based (meth) acrylate represented by Chemical Formula 1 has excellent compatibility when mixed with the thio-ene composition, and contains a reactive group, thereby ensuring the reliability of the prepared composition.

In addition, the organophosphite-based (meth) acrylate represented by Formula 1 may be present in the form of one (meth) acrylate or a mixture of two or more.

In addition, the organophosphite-based (meth) acrylate represented by the general formula (1) includes a methacroyl oxy ethyl dihydrogen phosphite and di metaacroyl oxy ethyl hydrogen phosphite mixture; Acroyl oxy ethyl dihydrogen phosphite and dichloroyloxyethyl hydrogen phosphite mixture; A mixture of methacroyl oxy propyl dihydrogen phosphite and di metaacroyloxypropyl hydrogen phosphite; Acroyl oxy propyl dihydrogen phosphite and dichloroyloxypropyl hydrogen phosphite mixture; A mixture of methacroyl oxy butyl dihydrogen phosphite and di metaacroyloxybutyl hydrogen phosphite; And acroyl oxy butyl dihydrogen phosphite and di acroyloxybutyl hydrogen phosphite mixture. Preferably, a mixture of metaacroyl oxy ethyl dihydrogen phosphite and di metaacroyl oxy ethyl hydrogen phosphite; A mixture of methacroyl oxy propyl dihydrogen phosphite and meta di acroyloxypropyl hydrogen phosphite; And acroyl oxy butyl dihydrogen phosphite and di acroyloxybutyl hydrogen phosphite mixture.

In addition, the organophosphite-based (meth) acrylate represented by the general formula (1) is 0.01 to 5% by weight, preferably 0.05 to 3% by weight, more preferably 0.1 based on the total weight of the photocurable resin composition. To 2% by weight. If it is less than the above range, stability of the thio-ene composition cannot be ensured, and if it is more than the above range, water absorption is large and cannot be applied to a display material vulnerable to moisture.

In the present invention, the phenolic compound represented by Formula 2 or Formula 3 may act as a radical polymerization inhibitor, thereby further securing the storage stability of the thio-ene composition.

The phenolic compound represented by Formula 2 or Formula 3 may be a compound having a benzene ring or a naphthalene ring having one or more hydroxyl groups bonded thereto, and more preferably, a compound of a benzene ring or a naphthalene ring having two or more hydroxyl groups bonded thereto.

In addition, the phenolic compound represented by Formula 2 or Formula 3, Pyrogallol (Pyrogallol); Propyl-3,4,5trihydroxybenzene; 2,4,5-trihydroxybutyrophenone; Hydroquinone; Catechol; t-butyl catechol; Gallic acid; Gallic acid ester compounds (ethyl gallate, propyl gallate, octyl gallate, dodecyl calate, etc.); Toluhydroquinone; Monot-butylhydro quinone; 2,5-di-t-butylhydroquinone; 4-methoxyphenol; 4-methoxy-1-naphthol; 1,4-dihydroxynaphthalene; 4-methoxy-2-methyl-1-naphthol; 4-methoxy-3-methyl-naphthol; 1,2-dihydroxynaphthalene; 1,4-dimethoxy-2-naphthol; And 1,4-dihydroxy-2-methylnaphthalene; and may be at least one selected from the group consisting of: pyrogarol, toluhydroquinone, 4-methoxyphenol, and 4-methoxy-1-naphthol It may be one or more selected from the group consisting of.

In addition, the phenolic compound represented by Formula 2 or Formula 3, based on the total weight of the photocurable resin composition, 0.01 to 5% by weight, preferably 0.05 to 3% by weight, more preferably 0.1 to 2% by weight Can be. If it is less than the above range, it is not possible to ensure the stability of the thio-ene composition, and if it is above the above range, dissolution may not be completed due to the properties of the chemical structure, which may cause a problem in appearance or a problem in curability during ultraviolet irradiation.

In the present invention, the (meth) acrylate compound (A) is a (meth) acrylated monomer, a urethane (meth) acrylate oligomer, a polyester (meth) acrylate oligomer, and an epoxy (meth) acrylate oligomer It may be one or more selected from the group consisting of, but is not limited thereto, and any (meth) acrylate compound commonly used in the art may be used without limitation.

The (meth) acrylated monomer may be prepared by ester condensation of an aliphatic alcohol and (meth) acrylic acid. Depending on the number of aliphatic alcohols may be mono-, bi-, tri-, tetra-, tetra- or hexa- (meth) acrylate monomers. Representative examples include (meth) acrylic acid, ethylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate ester, isosorbide di (meth) acrylate, tris (2-hydroxyethyl) isocy Anurate tri (meth) acrylate and di (meth) acrylate, alkyl of acrylic acid or methacrylic acid (e.g. isobonyl, isodecyl, isobutyl, n-butyl, t-butyl, methyl, ethyl, tetrahydrofur Furyl, cyclohexyl, n-hexyl, iso-octyl, 2-ethylhexyl, n-lauryl, octyl or decyl), hydroxy alkyl (such as 2-hydroxyethyl and hydroxy propyl) ester (meth) acrylates, Phenoxyethyl (meth) acrylate, nonylphenol ethoxylate mono (meth) acrylate, 2-(-2-ethoxyethoxy) ethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, Butylene glycol di (meth) acrylate and Li (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethoxylated and / or propoxylated hexanediol di (meth) acrylate, ethoxylated bisphenol A diacrylate, sorbitol di (meth) Acrylate, glycerol tri (meth) acrylate and ethoxylated and / or propoxylated derivatives thereof, bisphenol A di (meth) acrylate and ethoxylated and / or propoxylated derivatives thereof, tricyclodecanedi (meth) acrylic Latex, tricyclodecanedimethanol di (meth) acrylate, pentaerythritol di (meth) acrylate and tri (meth) acrylate and tetra (meth) acrylate and ethoxylated and / or propoxylated derivatives thereof, ethylene Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate , Propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentylglycol di (meth) acrylate, ethoxylated and / or propoxylated neo Pentylglycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, 4,4'-bis (2-acryloyloxyethoxy) diphenylpropane, trimethylolpropane di (meth) acrylate, trimethyl Allpropane tri (meth) acrylate and ethoxylated and / or propoxylated derivatives thereof, dipentaerythritol tetra (meth) acrylate and penta (meth) acrylate and hexa (meth) acrylate and ethoxylation thereof Or propoxylated derivatives.

Moreover, the said urethane (meth) acrylate generally has a (meth) acrylate functional group of 2-15. Urethane (meth) acrylates are generally one or more polyisocyanates, one or more (meth) acrylate functional groups containing one or more (generally one) reactive groups that can react with isocyanate groups, and, optionally, can react with isocyanate groups From the reaction of one or more compounds containing two or more reactive groups. Reactive groups that can react with isocyanate groups are generally hydroxyl groups. Examples include Miramer® PU240, Miramer® PU256, Miramer® PU2100, Miramer® UA5095, Miramer® PU3200, Miramer® PU3210, Miramer® PU330, Miramer® PU340, Miramer® PU370, Miramer® PU3410, Miramer® PU664, Miramer® SC2100 , Miramer® SC2153, Miramer® SC2152 (above Miwon Specialty Chemicals), EBECRYL®4883, EBECRYL®9384, EBECRYL®1290, EBECRYL 220® (above Alex), UV-3510TL, UV3000B, UV3310B, UV-7510B, Products such as UV-7600B and UV-1700B (above Nippon Kosei Co., Ltd.) can be purchased and used selectively.

In addition, the polyester (meth) acrylates are generally obtained from ester reactions with one or more polyols and one or more (meth) acrylic acids. Acrylic acid and methacrylic acid are preferably used alone or in combination. Suitable polyester (meth) acrylates are, for example, aliphatic or aromatic polyhydric polyols which are all esterified with (meth) acrylic acid and may contain residual hydroxyl functionality in the molecule and are easy and suitable for characterizing the product. The way is to measure its hydroxyl number (mgKOH / g). Suitable are partial or total esterification products of (meth) acrylic acid and di-hexavalent polyols and mixtures thereof. Furthermore, reaction products of such polyols with ethylene oxide and / or propylene oxide or mixtures thereof, or reaction products of such polyols with lactones and lactide can be used. Examples include Miramer® PS420, Miramer® PS430, Miramer® PS460, Miramer® PS610 (above Miwon Specialty Chemicals), EBECRYL®870, EBECRYL®657, EBECRYL®450, EBECRYL® 800, EBECRYL®884, EBECRYL®885 Products such as EBECRYL®810 and EBECRYL® 830 (above Alex) are available for optional use.

In addition, the epoxy (meth) acrylates are generally obtained from the reaction of at least one polyepoxy compound and at least one (meth) acrylic acid. Acrylic acid and methacrylic acid are preferably used alone or in combination. Examples of suitable epoxy (meth) acrylate oligomers are di (meth) acrylates of diglycidyl ethers of bisphenol A and variants thereof, for example EBECRYL® 3700 or EBECRYL® 600, EBECRYL® 3701, EBECRYL®3703 , EBECRYL® 3708, EBECRYL® 3720 and EBECRYL® 3639 (above Alex), Miramer® PE210, Miramer® PE2120A, Miramer® PE250 (above Miwon Specialty Chemicals).

The (meth) acrylate compound (A) may be 50 to 80% by weight, preferably 50 to 75% by weight, more preferably 50 to 70% by weight based on the total weight of the photocurable resin composition. If it is less than the above range, it is not possible to ensure the stability of the thio-ene composition, and if it is above the above range, dissolution may not be completed due to the properties of the chemical structure, which may cause a problem in appearance or a problem in curability during ultraviolet irradiation.

In the present invention, the thiol compound (B) containing two or more mercapto groups (-SH) in the one molecule comprises a primary and a secondary mercapto group (-SH), at least two functional groups in the molecule- It may include SH.

Thiol compound (B) comprising two or more mercapto groups (-SH) in the one molecule is 15 to 45% by weight, preferably 18 to 42% by weight, based on the total weight of the photocurable resin composition Preferably 20 to 40% by weight. If it is less than the above range, it is not possible to ensure the stability of the thio-ene composition, and if it is above the above range, dissolution may not be completed due to the properties of the chemical structure, which may cause a problem in appearance or a problem in curability during ultraviolet irradiation.

In addition, the thiol compound (B) containing two or more mercapto groups (-SH) in the one molecule is 0.2 to 1.0 equivalents, more preferably 0.3 to 1 equivalent to 1 equivalent of the (meth) acrylate mixture (A) It may be included in 0.8 equivalent. If it is less than the above range, it is not possible to ensure the stability of the thio-ene composition, and if it is above the above range, dissolution may not be completed due to the properties of the chemical structure, which may cause a problem in appearance or a problem in curability during ultraviolet irradiation.

In addition, the thiol compound (B) comprising two or more mercapto groups in the one molecule may be one or more selected from the group consisting of polythiol, aliphatic polythiol, aromatic polythiol and ester polythiol.

In the present invention, the photoinitiator (C) may induce the formation of the photocurable resin composition through photocuring.

The photoinitiator (C) may include at least one selected from the group consisting of acylphosphine oxide-based photoinitiators and photoinitiators other than acylphosphine oxide-based.

The acylphosphine oxide-based photoinitiator has a characteristic of exhibiting activity at long wavelengths, and includes bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Izem Corporation Igacure 819); 2,4,6-tribenzoyldiphenylphosphine oxide (Izem Corporation Tarocure TPO); And ethyl-2,4,6-triethylbenzoylphenylphosphinate (Izem Corporation TPO-L); and one or more selected from the group consisting of. Photoinitiators other than the acylphosphine oxide-based photoinitiator hydroxy alkylphenone (α-hydroxyalkylphenone); α-aminoalkylphenone-based photoinitiators; Benzoineether type photoinitiator; α, α-dialkoxyacetophenone (α, α-Dialkoxyacetophenone) -based photoinitiators; And a phenylglyoxylate-based photoinitiator; may be at least one selected from the group consisting of 1-hydroxy-cyclohexyl-phenyl-ketone (Igemsar, Igacure), preferably α-hydroxyalkylphenone-based. 184) and 2-hydroxy-2-methyl-1-phenyl-1-propanone (Igem Corporation, Igacure 1173).

The total amount of the photoinitiator (C) may be 0.1 to 10% by weight, preferably 0.5 to 8% by weight, and more preferably 1 to 5% by weight, based on the total weight of the photocurable resin composition. If less than the above range, curing failure may occur, and if it exceeds the above range, problems with durability may occur due to yellowing and poor curing density.

In the present invention, the quantum dot particles (D) include, for example, a core layer and a shell layer located outside the core layer, wherein at least one of the core layer and the shell layer is selected from aluminum, silicon, titanium, magnesium, and zinc. Doped with at least one, the core layer may be one containing a III-V compound.

Group III-V compounds of the core layer are, for example, GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and a mixture thereof. ; Three-element compounds selected from the group consisting of GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs AlPSb, InNP, InNAs, InNSb, InPAs, InPSb and mixtures thereof; And an elemental compound selected from the group consisting of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, GaAlNP, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof.

In addition, the quantum dot particles (D), for example, In and P are included in the core layer, at least one selected from Zn, Se, and S is included in the shell layer, and a nonpolar ligand having 5 to 30 carbon atoms is added. It may be to include as.

In addition, in the quantum dot particles (D), blue light may be converted into green light or red light according to the particle size. The average particle diameter of the quantum dot particle (D) may be 1 to 100 nm, blue light is converted to green light as the average particle diameter is smaller within the range, blue light may be converted to red light as the average particle diameter is larger.

Specifically, the particles capable of converting blue light into green light have a particle diameter of 3 to 12 nm, preferably 5 to 10 nm, and a maximum absorption wavelength of 530 to 550 nm. In addition, the particles capable of converting the blue light into the red light have a particle diameter of 6 to 20 nm, preferably 8 to 15 nm, and a maximum absorption wavelength of 615 to 650 nm.

In addition, the quantum dot particles (D) may be included in 0.1 to 2% by weight, preferably 0.2 to 1.8% by weight, more preferably 0.5 to 1.5% by weight based on the total weight of the photocurable resin composition. If it is less than the above range, the luminous power may be lowered. If it is more than the above range, the luminous power may be excessive and thus may not be suitable as a material for display fields.

In addition, the quantum dot particles (D) is preferably used by mixing a ratio of particles that can convert blue light into green light and particles that can convert blue light into red light in a ratio of 3: 1 to 1: 1. When the quantum dot particles (D) are mixed and used in a ratio within the above range, color conversion of light is smoothly performed, and thus the luminous power may be excellent.

In the photocurable resin composition of the present invention, the scattering particles (E) may be used to secure color uniformity.

In general, in order for light to be scattered, the scattering effect of light may be increased as the difference between the refractive index of the scattering particles and the refractive index of the matrix resin after curing is increased. At this time, a matrix resin means the hardened | cured material of the photocurable resin composition except a scattering particle.

In the present invention, the difference in refractive index between the scattering particles (E) and the matrix resin after curing may be 0.05 to 0.3, preferably 0.1 to 0.2. If it is less than the above range, the internal scattering effect is halved, so the content of the scattering particles (E) must be increased, thereby reducing economic efficiency and lowering durability. In this case, the matrix resin means a thiol compound (B) containing two or more mercapto groups in the (meth) acrylate compound (A) and one molecule.

The scattering particles (E) are silica, alumina, silicon, silicon, alumina, titanium dioxide (TiO 2), zirconia (ZrO 2), barium sulfate, and zinc oxide (ZnO). It may be at least one particle selected from the group consisting of polymethyl methacrylate (Poly (methylmethacrylate), PMMA) and benzoguanamine-based polymer.

In addition, the average particle diameter of the scattering particles (E) may be 10 to 100 nm, preferably 15 to 95 nm, more preferably 20 to 90 nm. If it is less than the above range, the scattering effect is lowered and the color uniformity is not good. If it exceeds the above range, the scattering effect is excessive and the color uniformity is not good either.

In addition, the scattering particles (E) may be included in 0.1 to 15% by weight, preferably 0.2 to 10% by weight, more preferably 0.5 to 8% by weight based on the total weight of the photocurable resin composition. If it is less than the above range, the scattering effect is lowered and the color uniformity is not good. If it exceeds the above range, the scattering effect is excessive and the color uniformity is not good either.

In the present invention, the photocurable resin composition may have a viscosity change rate (ΔV) defined by Equation 1 below 2.0 or less:

<Equation 1>

ΔV = V ₂ / V ₁

In Equation 1, V ₁ is the initial viscosity at 25 ℃, V ₂ is the viscosity at 25 ℃ after storage for 30 days at 60 ℃.

Preferably, the viscosity change rate (ΔV) defined by Equation 1 may be 1 to 2.0, more preferably 1 to 1.5, and the smaller the viscosity within the prescribed range may be advantageous. If it exceeds the above range, the viscosity is excessively high, so that coating is difficult to uniformly during film coating, and thus it is difficult to use the display material as it is difficult to secure uniformity of brightness.

Photocurable  Manufacturing method of the resin composition

The present invention also provides a (S1) (meth) acrylate compound (A); Thiol compound (B) comprising two or more mercapto groups in one molecule; Photoinitiator (C); Organophosphate-based (meth) acrylates represented by Formula 1; And removing water from the mixture of the phenolic compound represented by the following Chemical Formula 2 or Chemical Formula 3; and a method of preparing a photocurable resin composition, and further after (S1), after (S2) ) The method may further include adding and mixing the quantum dot particles (D) and the scattering particles (E) to the mixture from which the moisture is removed:

<Formula 1>

R ₁ in Formula 1 is selected from Formula 1-1, Formula 1-2, Formula 1-3, and Formula 1-4, R ₂ is hydrogen or methyl, and n is an integer of 1 to 3:

<Formula 1-1>

<Formula 1-2>

<Formula 1-3>

<Formula 1-4>

X in Formulas 1-1 to 1-4 may be the same as or different from each other, and is an integer of 0 to 10; And

<Formula 2>

<Formula 3>

In Formula 2 or Formula 3, R ₃ to R ₉ may be each independently the same or different, hydrogen, -OH, -COOH, C ₁ to C ₁₀ linear or pulverized alkyl, C ₁ to C ₁₀ straight chain Or pulverized alkoxy alkyl, C ₁ to C ₁₀ linear or pulverized alkyl containing ester groups.

Hereinafter, the manufacturing method of the photocurable resin composition in each step will be described in more detail. The physical properties, types, and weights of the materials used in the method of preparing the photocurable resin composition are as described above.

(S1) step

In the step (S1), the (meth) acrylate compound (A); Thiol compound (B) comprising two or more mercapto groups in one molecule; And photoinitiators (C); Organophosphate (Organophosphate) -based (meth) acrylate represented by Formula 1; And phenol-based compounds represented by Formula 2 or Formula 3; moisture may be removed from the mixture.

The organophosphite-based (meth) acrylate represented by Formula 1 may be prepared by reacting a (meth) acrylate including a phosphorus pentoxide represented by the following Formula 4 with a hydroxyl group (-OH) represented by the following Formula 5. It may further be prepared by reacting water together:

<Formula 4>

; 및

; And

<Formula 5>

,

,

R ₁ in Formula 5 is selected from Formula 1-1, Formula 1-2, Formula 1-3, and Formula 1-4, and R ₂ is hydrogen or methyl:

<Formula 1-1>

<Formula 1-2>

,

,

<Formula 1-3>

,

,

<Formula 1-4>

,

,

In Formulas 1-1 to 1-4, X may be the same as or different from each other, and is an integer of 0 to 10.

For example, 1 to 8 moles of (meth) acrylate containing a hydroxyl group represented by Formula 5 and 0 to 2 moles of water may be reacted with respect to 1 mole of phosphorus pentoxide represented by Formula 4 above. Preferably, 3 to 6 moles of (meth) acrylate containing a hydroxyl group represented by Formula 5 and 1 to 2 moles of water may be reacted with respect to 1 mole of phosphorus pentoxide represented by Formula 4 above. At this time, the sum of the (meth) acrylate containing a hydroxyl group represented by the formula (5) and water may be preferably 6 to 8 moles. In addition, when 1 mole of phosphorus pentoxide represented by Formula 4 reacts with more than 2 moles, phosphoric acid that does not contain a (meth) acrylate functional group is formed, thereby organo represented by Formula 1 Cloudiness may occur when the phosphite-based (meth) acrylate is mixed with the thio-ene composition.

In addition, water may be removed after mixing the above materials, and the water removal may be performed under 20 to 150 ° C. temperature and 0.1 to 2 torr pressure, preferably 40 to 70 ° C. temperature and 0.5 to 1.5 torr pressure. It can be performed under. When the temperature is less than the above range or the pressure is above the above range, the removal of moisture is not smooth, so that the moisture may affect the quantum dot particles, and thus the luminance may be lowered, and color conversion may be difficult. Moreover, when temperature is more than the said range or a pressure is below the said range, process cost will increase, the viscosity change of the said photocurable resin composition will become large, the storage stability of the quantum dot composition to which the said photocurable resin composition is applied, and a viscosity will rise, The color of the composition may be altered, making it difficult to produce a uniform optical film, such as a quantum dot film, and reduce the color quality of the display.

In addition, through the water removal process, it is possible to minimize the moisture in the photocurable resin composition. The amount of water in the photocurable resin composition may be controlled to 200 ppm or less, preferably 100 ppm or less, more preferably 30 ppm or less through the water removal process. If the moisture is greater than the above range, the damage of the quantum dot particles may be generated by the moisture, and color conversion may not be desired, and partial decolorization may proceed. Ideally, it is ideal to completely remove the amount of water in the photocurable resin composition through the water removal process, but removing water completely may result in an increase in process cost or a decrease in productivity. Water may also be contained. In consideration of the process cost and productivity, the amount of water to be contained may include water in the range of 1 to 200 ppm, preferably 5 to 100 ppm, more preferably 10 to 30 ppm.

(S2) step

In the step (S2), after adding and mixing the quantum dot particles (D) and the scattering particles (E) to the mixture from which the water is removed, a photocurable resin composition may be obtained.

Optical film

This invention may also be related with the optical film containing a photocurable resin composition.

The optical film may include a coating layer of the photocurable resin composition on at least one surface of the substrate.

The substrate is not particularly limited as long as it can be used as the substrate of the optical film. For example, the substrate may be a polyethylene terephthalate film, polycarbonate film, polypropylene film, polyethylene film, polystyrene film or polyepoxy film.

The coating layer of the photocurable resin composition may be appropriately adjusted according to its use, for example, may be 50 to 100nm when applied to the field of transparent display.

In the present invention, the optical film may be a quantum dot film.

The optical film includes a first barrier layer; A second barrier layer; And a quantum dot layer positioned between the first barrier layer and the second barrier layer, wherein the quantum dot layer may be formed of the photocurable resin composition.

In the present invention, the quantum dot layer may be formed by the photocurable resin composition.

In general, nano-scale quantum dots are easily affected by external factors such as moisture or oxygen, and thus have a short lifespan.

In the present invention, in order to supplement and improve the problems of such quantum dots organophosphite-based (meth) acrylate represented by the formula (1); And a phenolic compound represented by Formula 2 or Formula 3; and a quantum dot layer made of a photocurable resin composition in the form of a composite, that is, a quantum dot-polymer composite.

In addition, in order to ensure the efficiency and color purity of the quantum dots included in the quantum dot layer made of the photocurable resin composition of the quantum dot-polymer composite, a layer serving as a passivation layer (passivation layer) on the surface of the quantum dot layer need.

In the quantum dot film according to the present invention, it may include a barrier layer for protecting the quantum dot layer from moisture or oxygen.

In the present invention, the barrier layer may be formed on both sides of the quantum dot layer, which are referred to as first and second barrier layers, respectively.

The barrier layer may include a substrate and a metal oxide deposited on at least one surface of the substrate.

The substrate is not particularly limited as long as it is a transparent substrate. Specifically, the substrate may be an optically transparent substrate, for example, a substrate having a wavelength of 400 nm to 700 nm and a transmittance of 90% or more.

The substrate is a polyester selected from poly (meth) acrylate, polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; Polyolefins selected from polycarbonates, polyethylenes and polypropylenes; Vinyl polymers selected from polyvinylacetate and polystyrene; Cyclic olefin polymers (COPs); Polyimide; Aliphatic or aromatic polyamides (eg, nylon, aramid, etc.); Polyether ether ketone; Polysulfones; Polyethersulfones; Polyamideimide; Polyetherimide; And thiolene polymers; may include one or more polymers selected from the group consisting of. Preferably, the substrate may include polyethylene terephthalate having excellent heat resistance and optical properties.

In addition, the metal oxide can be used by appropriately selecting the size and type within a range that does not affect the performance of other components such as light emission characteristics.

The metal oxide may be silicon oxide, silicon nitride, silicon carbide, silicon oxynitride, silicon oxycarbide, aluminum oxide, aluminum nitride, aluminum carbide, aluminum oxynitride, aluminum oxycarbide, titanium oxide, titanium nitride, It may be one or more selected from the group consisting of titanium carbide, titanium oxynitride and titanium oxycarbide.

In addition, the metal oxide may have a size of 0.05 to 10 μm, preferably 0.1 to 8 μm, more preferably 1 to 5 μm. If it is less than the above range, moisture and oxygen barrier properties may be lowered, and if it is above the above range, transparency may be lowered and it may be difficult to apply to a transparent display.

In addition, the metal oxide may be deposited on the substrate to a thickness of 0.01 to 2 ㎛, preferably 0.05 to 1 ㎛, more preferably 0.08 to 0.5 ㎛. If it is less than the above range, moisture and oxygen barrier properties may be lowered, and if it is above the above range, transparency may be lowered and it may be difficult to apply to a transparent display.

Manufacturing method of optical film

This invention also relates to the manufacturing method of the optical film containing the said photocurable resin composition.

An optical film can be manufactured by apply | coating a photocurable resin composition to at least one surface of the base material as mentioned above, hardening, and forming a coating layer. In this case, the curing may be ultraviolet curing.

The light source of the active energy ray used in the ultraviolet curing is not particularly limited, but specific examples include black light, UV-LED lamp, high pressure mercury lamp, pressurized mercury lamp, metal halide lamp, xenon lamp, and electrodeless discharge lamp. have. Of these light sources, black light and LED lamps (UV-LED lamps) are preferable in terms of safety and economy.

The light source irradiation amount of the active energy ray may be an amount sufficient for curing the photocurable resin composition, and may be selected according to the composition, amount, thickness, shape of the cured product to be formed, and the like. For example, when irradiating and hardening an ultraviolet-ray with respect to the thin film of the said photocurable resin composition (for example, the coating film formed by the apply | coating method), it can be set as the light quantity of 200 mJ / cm <2> or more and 5000 mJ / cm <2> or less, More preferably, the amount of light may be 500 mJ / cm 2 or more and 3000 mJ / cm 2 or less.

The present invention also, as described above, the first barrier layer; A second barrier layer; And a quantum dot layer positioned between the first barrier layer and the second barrier layer, the quantum dot layer comprising the photocurable resin composition.

The quantum dot film may be prepared by forming the photocurable resin composition coatings on the first barrier layer, laminating the second barrier layer, and then performing ultraviolet curing. The ultraviolet curing method is as described above.

Hereinafter, preferred examples are provided to help the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and various changes and modifications within the scope and spirit of the present invention are apparent to those skilled in the art. It goes without saying that changes and modifications belong to the appended claims.

Production Example : Quantum dots  Particle manufacturing

0.2 mmol of indium acetate, 0.6 mmol of palmitic acid and 10 mL of 1-octadecene were placed in a reactor and heated to 120 ° C. under vacuum. After several hours the atmosphere in the reactor was switched to nitrogen. After heating to 280 ° C., a mixed solution of 0.1 mmol of tris (trimethylsilyl) phosphine and 0.5 mL of trioctylphosphine was rapidly injected and reacted for 20 minutes. Acetone was added to the reaction solution cooled to room temperature rapidly, and the precipitate obtained by centrifugation was dispersed in toluene.

The obtained InP semiconductor nanocrystals had a particle size determined according to the reaction time and exhibited a UV maximum wavelength of 420 to 600 nm depending on the particle size. 0.3 mmol of zinc acetate (0.056 g), 0.6 mmol of oleic acid (0.189 g), and 10 mL of trioctylamine were added to a reaction flask and vacuum-treated at 120 ° C. for 10 minutes. The reaction flask was replaced with N ₂ and then heated to 220 ° C.

Toluene dispersion of InP semiconductor nanocrystals prepared above, 0.15 mL of 1-octadecane and 0.6 mmol of TOPS (sulfur dispersed / dissolved in trioctylphosphine) were added to the reaction flask and allowed to react at 30 ° C. for 30 minutes. After the reaction was completed, the reaction solution was rapidly cooled to room temperature to obtain a reaction product including InP / ZnS quantum dots.

Excess ethanol was added to the reaction product including the InP / ZnS quantum dots and centrifuged to remove excess organic matter present in the quantum dots. After centrifugation, the supernatant was discarded, and the centrifuged precipitate was dried, and then dispersed in toluene to measure UV-vis absorption spectra to confirm red light emission or green light emission. The particle size of the red light-emitting particles is 5 to 10 nm, the maximum peak of the absorption spectrum is 540 nm, the half width is 41 nm, the particle size of the green light emitting particles is 8 to 15 nm, the maximum peak of the absorption spectrum is 625 nm, half width. Was 45 nm. In the above method, each red or green light-emitting quantum dot particle dispersion was prepared.

Synthesis Example  One

Into a 1000 mL three-necked glass reactor equipped with a mechanical stirrer and a thermometer, 288.3 parts by weight (2.0 mol) of 2-hydroxypropyl methacrylate and 7.2 parts by weight (0.4 mol) of water were added and stirred and mixed. 113.6 parts by weight (0.4 mole) of phosphorus pentoxide was divided and added while paying attention to exotherm, and the internal temperature was adjusted so as not to exceed 40 ° C. metaacroyl oxypropyl dihydrogen phosphite (60%) and dimethacroyloxypropyl Hydrogen phosphite (40%) mixture was prepared. The chemical structure of the material was confirmed by H-NMR and FT-IR of FIG.

Synthesis Example  2

Into a 1000 mL three-necked glass reactor equipped with a mechanical stirrer and a thermometer, 248.6 parts (1.8 mol) of 4-hydroxy butyl acrylate and 10.8 parts (0.6 mol) of water were added, stirred and mixed. 113.6 parts by weight (0.4 mole) of phosphorus pentoxide was divided and added while paying attention to exotherm, and the internal temperature was controlled so as not to exceed 40 ° C., acroyl oxybutyl dihydrogen phosphite (70%) and dichloroyloxybutyl hydrogen A phosphite (30%) mixture was prepared. The chemical structure of the material was confirmed by H-NMR of FIG.

Synthesis Example  3

Into a 500 mL three-necked glass reactor equipped with a mechanical stirrer and a thermometer, 312.3 parts by weight (2.4 mol) of 2-hydroxyethyl methacrylate was added and stirred and mixed. 56.8 parts by weight (0.2 mol) of phosphorus pentoxide was divided and added while paying attention to exotherm, and the internal temperature was adjusted so as not to exceed 40 ° C. Methacroyl oxyethyl dihydrogen phosphite (50%) and dimethacroyloxyethyl Hydrogen phosphite (50%) mixture was prepared. The chemical structure of the material was confirmed by H-NMR of FIG.

Example  1 to 5 and Comparative example  1 to 4

(1) Preparation of photocurable resin composition

According to the composition as shown in Table 1, after mixing (meth) acrylate mixture (A), thiol mixture (B), photoinitiator (C), organophosphite compound and phenolic compound, 60 ℃, The water removal process was performed for 1 hour under 1 torr of reduced pressure conditions. However, Comparative Example 4 did not perform the water removal step.

Quantum dot particles (D) and scattering particles (E) were added to the mixture from which the moisture was removed, and uniformly mixed at a speed of 500 rpm using a high speed stirrer to prepare a photocurable resin composition. In this case, the quantum dot particles (D) was used in the weight ratio of red light emitting particles and blue light emitting particles 3: 7.

(2) quantum dot film manufacturing

In order to form the first and second barrier layers, a polyethylene terephthalate film (Toyobo Corporation A4300) having a thickness of 50 μm in which silicon oxide was deposited to a thickness of 0.1 μm was used as the first and second films.

The photocurable resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 4, respectively, were filtered through a 0.2 μm Teflon filter and depressurized for 30 minutes to completely remove bubbles.

After coating the photocurable resin composition on one surface of the first film by using a micro bar, the second film was laminated on the photocurable resin composition coating layer to perform ultraviolet curing. A rubber roll was used to prevent bubbles from occurring during the lamination. In addition, the UV curing apparatus used a Lithzen UV curing machine (UVMH1001) equipped with a metal halide lamp, the amount of light in the UVA region measured using EIT's UV Puck II was 1500 mJ. The thickness of the quantum dot layer formed by curing the photocurable resin composition was maintained at 50 ± 2 ㎛.

Raw material (unit: weight%) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 (Meth) acrylate mixture (A) M300 30 30 50 - 66 32 30 67 30 M200 20 20 15 50 - 20 20 - 20 EB-600 5 - - 7 - 5 - - 5 EB-830 - 6 10 - - - 6 - - Thiol Mixture (B) PEMP 40 - 20 35 30 40 - 30 40 PE-1 - 40 - - - - 40 - - Photoinitiator (C) I-184 1.5 1.5 1.5 One 1.5 1.5 1.5 1.5 1.5 D-TPO One 1.4 1.5 1.5 1.5 One 1.5 1.5 One Quantum Dot Particles (D) Production Example 2 2 2 2 2 2 2 2 2 Scattering Particles (E) FINEX 30 3 3 3 3 3 3 3 3 3 Organophosphite compounds Synthesis Example 1 2 One - - - - One - 2 Synthesis Example 2 - - 1.5 - - - - - - Synthesis Example 3 - - - 5 1.5 - - - - Phenolic Compound HQMME 0.5 0.1 - - 0.5 0.5 - - 0.5 THQ - - 0.5 0.5 - - - - - Water removal process ○ ○ ○ ○ ○ ○ ○ ○ X

M300: trimethylolpropane triacrylate (miwon specialty chemical company)

M200: hexanediol diacrylate (Miwon Specialty Chemicals Co., Ltd.)

EB-600: Bisphenol A epoxy acrylate (Alex Corporation)

EB-830: Polyester 6-functional acrylate (Alex Corporation)

PEMP: pentaerythritol tetramer captoacetate (SC organic chemistry company)

PE-1: pentaerythritol tetrakis (3-mercaptobutylate) (Showa Denko)

I-184: 1-hydroxycyclohexyl-phenyl-ketone (IGM Corporation)

D-TPO: 2,4,6-tribenzoyldiphenylphosphine oxide (IGM Corporation)

HQMME: methoxy hydroquinone (eastman company)

THQ: toluhydroquinone (eastman company)

FINEX 30: Zinc oxide (Sakai Chemical, average particle diameter 35 nm)

Experimental Example  One

The photocurable resin compositions or quantum dot films prepared in Examples 1 to 5 and Comparative Examples 1 to 4, respectively, were measured for viscosity, moisture content, adhesion between barrier films, luminance, and edge discoloration.

(1) viscosity measurement

Viscosity was measured using a Brufields Corporation DV-2 + model connected to a constant temperature bath. The temperature of 25 degreeC was hold | maintained, 1 mL of photocurable resin composition samples were taken, and the viscosity value was shown. After leaving for 10 days in the 60 degreeC oven and the initial viscosity measured after mixing (V2), the ratio (V2 / V1) of the viscosity value was shown and the storage stability was confirmed.

(2) Water content measurement

The moisture content of the photocurable resin composition sample was measured using a vaporization moisture meter. The evaporator used Kyoto Electronics' ADP-611 and the Karl Fischer moisture meter combined the product of the company's MKC-710M to measure the amount of evaporated water. About 0.1 g of the photocurable resin composition was measured for 10 minutes at a heating temperature of 120 ° C. and 99.999% ultrapure nitrogen at a flow rate of 100 mL / min to determine the amount of vaporized water.

(3) Adhesion between barrier films

For the produced quantum dot film, when peeling between two films (first and second films) by hand, if the film (first and second films) is broken and the film (first and second films) is broken, it is determined that the adhesive strength is excellent and is indicated by O, If the film is difficult to peel off but there is no film breakage, it is indicated by △.

(4) luminance measurement

Cut the prepared quantum dot film to A4 size and mount it to the center of the backlight of Samsung SUHD TV JS6500 model and apply power to it, and then use the luminance meter (CS-2000, Minolta) to measure the brightness (Y) of 13 spots. It measured and calculated | required the average value. Compared to the initial luminance, after 250 hours of heat resistance (80 ° C.) and high temperature and high humidity (90 ° C., 60%), the luminance (Y) and the change rate (Y (%)) relative to the initial luminance were measured based on this.

(5) Edge discoloration

After cutting the quantum dot film to A4 size and leaving the film for 48 hours under the condition of 85 ℃ and 85% humidity, it is attached to the center of the backlight of the Samsung SUHD TV JS6500 model, and power is applied. The presence or absence of color omission was checked by visual observation, and if there was no color omission, ○, if there was a certain color omission on two or more sides of the slope,?

Table 2 below shows the viscosity, moisture content, adhesion between barrier films, brightness, and edge decolorization of the photocurable resin compositions or quantum dot films prepared in Examples 1 to 5 and Comparative Examples 1 to 4, respectively, according to the above method. It will show the result of whether or not.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Moisture content
(ppm) 15 10 11 27 12 16 14 16 630 Viscosity change
(V2 / V1) 1.2 1.3 1.1 1.0 1.5 Gelation 3.1 Gelation 1.7 Adhesion Between Barrier Films ○ ○ ○ △ ○ △ △ X △ Initial luminance Y (cd / ㎡) 592.9 590.4 593.1 590.3 590.1 588.6 589.4 590.1 593.1 High temperature luminance
(Y (%)) 590.1
(99.5) 587.3
(99.5) 590.1
(99.5) 588.7
(99.7) 587.9
(99.6) 501.6
(85.2) 499.8
(84.8) 485.6
(82.3) 440.1
(74.2) High temperature and high humidity brightness
(Y (%)) 527.4 (89.0) 520.9
(88.2) 522.7
(88.1) 518.6
(87.9) 519.9
(88.1) 412.3
(70.0) 409.4
(69.5) 400.5
(67.9) 374.4
(63.1) Edge bleaching ◎ ◎ ◎ ○ ◎ △ △ △ X

Referring to Table 2, the viscosity change of the photocurable resin composition and the quantum dot film of Examples 1 to 5, in which all raw materials are contained in an appropriate amount, is excellent in adhesion between the barrier films and brightness under high temperature and high humidity, On the other hand, Comparative Examples 1 and 3, in which the organophosphate metal acrylate-based material represented by Chemical Formula 1 is not contained, are gelled, and the adhesion between the barrier films and the brightness under high temperature and high humidity are not observed. It was not good and it confirmed that some discoloration occurred.

In addition, Comparative Example 2, which does not contain the phenolic compound material represented by Formula 2 or Formula 3, showed that the viscosity change was slightly higher, the adhesion between the barrier films and the high temperature and high humidity luminance were significantly lowered, and some decolorization occurred.

In addition, Comparative Example 4, which was not subjected to the water process, also exhibited a deterioration in overall physical properties, particularly a high temperature, high humidity brightness, and a significant discoloration.

Claims (13)

(Meth) acrylate compound (A); Thiol compound (B) comprising two or more mercapto groups in one molecule; Photoinitiator (C); And a quantum dot particle (D);
The quantum dot particles (D) include particles capable of converting blue light into green light and particles capable of converting blue light into red light, and particles capable of converting blue light into green light have a particle diameter of 3 to 12 nm. Particles capable of changing blue light to red light have a particle diameter of 6 to 20 nm,
Organophosphate-based (meth) acrylates represented by Formula 1; And a phenolic compound represented by Formula 2 or Formula 3 below: Photocurable resin composition comprising:
<Formula 1>

In Formula 1, R ₁ is selected from Formulas 1-1 to 1-4, R ₂ is hydrogen or methyl, and n is an integer of 1 to 3:
<Formula 1-1>

<Formula 1-2>

<Formula 1-3>

<Formula 1-4>

X in Formulas 1-1 to 1-4 may be the same as or different from each other, and is an integer of 0 to 10; And
<Formula 2>

<Formula 3>

In Formula 2 or Formula 3, R ₃ to R ₉ may be each independently the same or different, hydrogen, -OH, -COOH, C ₁ to C ₁₀ linear or pulverized alkyl, C ₁ to C ₁₀ straight chain Or branched alkoxy alkyl, or C1 to C10 straight chain or branched alkyl containing an ester group. The method of claim 1,
The photocurable resin composition,
50 to 80% by weight of the (meth) acrylate compound (A);
15 to 45 wt% of a thiol compound (B) comprising two or more mercapto groups in one molecule;
0.1 to 10 weight percent of photoinitiator (C);
0.1 to 2 wt% of quantum dot particles (D);
0.01 to 5 wt% of an organophosphate-based (meth) acrylate represented by Formula 1; And
0.01 to 5 wt% of a phenolic compound represented by Formula 2 or Formula 3 below; Photocurable resin composition comprising a. The method of claim 1,
The photocurable resin composition containing 0.1-1.2 equivalents of the thiol compound (B) containing 2 or more mercapto group in the said 1 molecule with respect to 1 equivalent of said (meth) acrylate compound (A). The method of claim 1,
The (meth) acrylate compound (A) is selected from the group consisting of (meth) acrylated monomers, urethane (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and epoxy (meth) acrylate oligomers. Photocurable resin composition which is a species or more. The method of claim 1,
The thiol compound (B) comprising two or more mercapto groups in one molecule is at least one selected from the group consisting of polythiol, aliphatic polythiol, aromatic polythiol and ester polythiol, photocurable resin composition. The method of claim 1,
The photoinitiator (C) is a photocurable resin composition comprising at least one selected from the group consisting of photoinitiators other than acylphosphine oxide-based photoinitiator and acylphosphine oxide (Acylphosphine oxide) -based. The method of claim 1,
Said photocurable resin composition is what further contains scattering particle | grains (E). The method of claim 7, wherein
The scattering particles (E) will be included in 0.1 to 15% by weight based on the total weight of the photocurable resin composition, the photocurable resin composition. The method of claim 1,
The quantum dot particle (D) includes a core layer and a shell layer located outside the core layer, at least one of the core layer and the shell layer is doped with at least one of aluminum, silicon, titanium, magnesium, and zinc, and the core layer The photocurable resin composition containing silver III-V compound. The method of claim 7, wherein
The scattering particles (E) are silica (Silica), alumina (Alumina), silicon (Silicon), titanium dioxide (TiO ₂ ), zirconia (ZrO ₂ ), barium sulfate (Zium oxide), zinc oxide (ZnO), polymethyl At least one selected from the group consisting of methyl methacrylate (Poly (methylmethacrylate), PMMA) and benzoguanamine-based polymers,
The photocurable resin composition which is particle | grains whose average particle diameter is 10-100 nm. The method of claim 1,
The photocurable resin composition is a photocurable resin composition, the viscosity change rate (ΔV) defined by the following formula 1 is 2.0 or less:
<Equation 1>
ΔV = V ₂ / V ₁
In Formula 1, V ₁ is the initial viscosity at 25 ℃, V ₂ is the viscosity at 25 ℃ after storage for 30 days at 60 ℃. The method of claim 1,
Said photocurable resin composition is water containing 200 ppm or less, photocurable resin composition. The method of claim 1,
The quantum dot particles (D) is a photocurable resin composition comprising particles that can convert the blue light into green light and particles that can convert blue light into red light in a weight ratio of 3: 1 to 1: 1.

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