KR102152125B1 - Composition for optical material comprising a ester polythiol mixture, Quantum dot film, Backlight unit, and Liquid crystal display - Google Patents

Abstract

[화학식 1]

[화학식 2]

The present invention is an ester polythiol compound represented by the following formula (1), and
It includes an ester polythiol compound containing a thioester functional group represented by the following formula (2),
The composition for an optical material has a P value of 1.03 to 1.07 calculated by using the SH value (g/eq.) α measured by wet titration and the theoretically calculated SH value (g/eq.) β. It provides a composition for an optical material, characterized in that:
[Equation 2]

[Formula 1]

[Formula 2]

Description

Composition for optical material comprising a ester polythiol mixture, quantum dot film, backlight unit, and liquid crystal display

The present invention relates to a composition for an optical material comprising an ester polythiol mixture, a method for preparing the ester polythiol mixture, a quantum dot film, a backlight unit, and a liquid crystal display.

In line with the recent information age, the display field has also developed rapidly, and in response to this, it is a liquid crystal display (LCD) as a flat panel display (FPD) with advantages of thinner, lighter, and low power consumption. , Plasma display device (PDP, Plasma Display Panel device), electroluminescence display device (ELD, ElectroLuminescence Display), field emission display device (FED, Field Emission Display), etc., were introduced, and the existing CRT (Cathode Ray Tube) was introduced. It is rapidly being replaced and in the spotlight.

Since the liquid crystal display is a light-receiving type display device in which light is incident from the outside to form an image, and cannot emit light by itself, a light source for providing light is essentially required. Conventionally, a cold cathode fluorescent lamp (CCFL) has been mainly used as a light source of a liquid crystal display device, but the cold cathode fluorescent lamp has a problem in that it is difficult to secure uniformity of luminance and color purity when the device becomes large. There is this.

Accordingly, in recent years, a three-color light emitting diode (LED) has been used as a light source of a liquid crystal display instead of a cold cathode fluorescent lamp. When a three-color LED is used as a light source, there is an advantage in that high color purity can be reproduced and a high-quality image can be realized, but there is a disadvantage in that the manufacturing cost is increased because the price is very high. Accordingly, technologies for implementing white light by converting blue light into red light and green light using a blue light-emitting diode, which is relatively inexpensive as a light source, and a light conversion film including a quantum dot (QD), have been proposed.

The quantum dot (QD) has a characteristic of being oxidized by oxygen or moisture. Therefore, the oxygen and moisture barrier of the light conversion film including quantum dots is very important. Therefore, the light conversion film is manufactured by attaching a barrier film to the upper and lower surfaces. However, since a separate barrier means is not included in the side portion of the film, oxygen or moisture penetrates through the side portion, so efforts have been made to form a quantum dot layer using a matrix resin having a low transmittance for oxygen and moisture.

In addition, in the case of a matrix including quantum dots, shrinkage during curing causes a change in the shape of the quantum dot layer in many cases, and a problem of weakening durability due to weak adhesion to the substrate interface is exposed, and solutions for this are being sought.

As a conventional technique proposed to solve the above problems, Japanese Patent No. JP 4820865 has 100% of the total peak area of mercapto carboxylic acid and its intermolecular condensation thioester compound in high-speed liquid chromatography (HPLC) measurement. In the case of, there is provided a method for producing a pentaerythritol mercaptocarboxylic acid ester by reacting a mercaptocarboxylic acid having a content of 5% or less (area percentage) of a condensed thioester compound between two molecules and pentaerythritol. However, in the case of manufacturing with an impurity content of 5% or less, there is a disadvantage in that the manufacturing cost increases due to the refining process and the shrinkage rate increases during the curing process, thereby reducing the interfacial adhesion.

In addition, Korean Patent Registration No. KR 10-1363198 discloses pentaerythritol mercaptocarboxylic acid whose content is 1.0% by weight or less in total when it does not contain alkali metal and alkaline earth metal, or contains at least one of them. Provides a method for producing an ester. However, even if impurities in pentaerythritol are reduced, the color of the optical material is not greatly improved or fairness is not improved. However, the purification process for removing the metallic impurities greatly increases the manufacturing cost, and thus it is difficult to view as a preferred method.

Korean Patent Registration No. KR 10-1363198

In the case of artificially generating a specific side-reactant rather than increasing the purity by removing impurities in the preparation of the ester polythiol compound, the present inventors believe that the composition for an optical material and the shrinkage rate of the optical film using the same, adhesion between the substrate interface, and moisture or oxygen The present invention was completed by finding that the physical properties for prevention of penetration of and the like are further improved.

Therefore, it is an object of the present invention to provide a composition for an optical material that can be used in applications such as quantum dot film production because of its low shrinkage, excellent adhesion between substrate interfaces, and excellent moisture or oxygen intrusion prevention function.

In addition, it is an object of the present invention to provide a manufacturing method capable of simply preparing an ester polythiol mixture in one step.

In addition, the present invention is to provide a quantum dot film, a backlight unit, and a liquid crystal display device that exhibits excellent luminance in a high temperature and high humidity environment, and has excellent durability by preventing edge discoloration, by using the composition for an optical material. do.

In order to achieve the above object, the present invention,

An ester polythiol compound represented by the following formula (1), and

It provides a composition for an optical material comprising an ester polythiol compound containing a thioester functional group represented by the following formula (2):

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,

A is a C1 ~ C12 aliphatic hydrocarbon group, each independently containing or not containing an unsaturated group, of a linear, branched or cyclic, hetero group,

R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or a C1 to C5 alkyl group,

k and l are each independently an integer of 0 to 3,

o is a natural number from 2 to 6, p is a natural number from 0 to 5, q is a natural number from 1 to 6, p+q = a natural number from 2 to 6,

m and n are each independently a natural number of 1 to 5,

The alkylene groups represented by m and n may be substituted or unsubstituted with C1 to C5.

In addition, the present invention

A method of preparing a compound represented by Formula 1 and a compound represented by Formula 2 in one step by condensation ester reaction of a compound represented by the following Formula 3 and a compound represented by Formula 4,

An ester polythiol mixture, characterized in that the water produced by condensation is removed using an azeotropic distillation method, but a process of continuously inducing a positive reaction by removing 95 to 110% of water of the theoretical dehydration amount to the outside by dehydrating it. Provides a method of manufacturing:

[Formula 3]

[Formula 4]

In Chemical Formula 3 and Chemical Formula 4

A is a C1-C12 aliphatic hydrocarbon group, each independently containing or not containing an unsaturated group, of a linear, branched, or cyclic, hetero group, and R ₁ and R ₂ is each independently hydrogen or a C1 to C5 alkyl group,

x is a natural number from 2 to 6,

m is a natural number from 1 to 5,

The alkylene groups represented by m may be substituted or unsubstituted with C1 to C5.

In addition, the present invention

A 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 provides a quantum dot film, characterized in that formed by the composition for an optical material of the present invention including quantum dots.

In addition, the present invention

It provides a backlight unit including the quantum dot film and a liquid crystal display device including the backlight unit.

The composition for an optical material of the present invention has a small shrinkage, excellent adhesion between substrate interfaces, and excellent function of preventing penetration of moisture or oxygen, so that it can be usefully used in applications such as manufacturing a quantum dot film.

In addition, the method for preparing an ester polythiol mixture of the present invention provides an effect of simply preparing an ester polythiol mixture in a single process.

In addition, the quantum dot film, the backlight unit and the liquid crystal display of the present invention exhibit excellent luminance in a high temperature and high humidity environment by using the composition for an optical material, and provide excellent durability by preventing edge discoloration.

1 to 4 are graphs showing high-speed liquid chromatography (HPLC) analysis spectra of ester polythiol mixtures prepared in Synthesis Examples 1 to 4 of the present invention.

Hereinafter, the present invention will be described in detail.

In the case of artificially generating a specific side-reactant, rather than increasing the purity by removing impurities in the preparation of the ester polythiol compound, the present inventors believe that the composition for an optical material and the shrinkage rate of the optical film using the same, adhesion between the substrate interface, and moisture or oxygen The present invention was completed by finding that the physical properties for prevention of penetration of and the like are further improved.

In general, ester polythiol compounds can be prepared by reacting a polyhydric aliphatic alcohol with a mercapto alkyl carboxylic acid having a carboxyl group and a thiol group in one molecule. That is, an ester polythiol compound containing an ester group is synthesized through a condensation ester reaction of an aliphatic alcohol and a carboxyl group, and water is produced as a by-product.

The present inventors have carried out the condensation ester reaction as an overreaction, so that the carboxyl group of the unreacted mercapto alkyl carboxylic acid with the thiol functional group of the ester polythiol compound already prepared together with the ester polythiol compound (compound of formula 1) By obtaining an ester polythiol compound containing a thioester group (a compound of the following formula 2) by a side reaction, an ester polythiol compound (a compound of the following formula 1) and an ester polythiol compound containing a thioester group (a compound of the following formula 2) ) To complete the present invention by preparing a composition for an optical material containing. The ester polythiol compound (the compound of Formula 1) and the ester polythiol compound (compound of Formula 2) containing a thioester group may be separately prepared and mixed.

The present invention is an ester polythiol compound represented by the following formula (1), and

It relates to a composition for an optical material comprising an ester polythiol compound containing a thioester group represented by the following Formula 2:

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,

A is each independently a linear, branched, or cyclic, C1-C12 aliphatic hydrocarbon group containing or not containing an unsaturated group, and

R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or a C1 to C5 alkyl group,

k and l are each independently an integer of 0 to 3,

o is a natural number from 2 to 6, p is a natural number from 0 to 5, q is a natural number from 1 to 6, p+q = a natural number from 2 to 6,

m and n are each independently a natural number of 1 to 5,

The alkylene groups represented by m and n may be substituted or unsubstituted with C1 to C5.

The alkylene groups represented by m and n may be substituted or unsubstituted with C1 to C5, and the C1 to C5 alkyl group may be linear or branched.

In one embodiment of the present invention, the weight ratio of the ester polythiol compound of Formula 1 and the ester polythiol compound including the thioester functional group of Formula 2 may be 1.80 to 2.30:1.

In addition, when the composition for an optical material is analyzed by high-speed liquid chromatography (HPLC), the peak area of the ester polythiol compound of Formula 1 and the thioester functional group of Formula 2 are included in the high-speed liquid chromatography (HPLC) spectrum. As for the peak area of the ester polythiol compound, an X value calculated by Equation 1 below may satisfy 1.80 to 2.30. Since the value obtained by dividing the peak area of each compound by the total peak area is the same as the weight ratio of each compound, the value of X in Formula 1 is a polythiol compound containing an ester polythiol of Formula 1 and a thioester group of Formula 2 It is equal to the weight ratio of.

[Equation 1]

X = the sum of the peak areas of the ester polythiol compound of Formula 1 / the sum of the peak areas of the polythiol compound containing the thioester group of Formula 2

The “/” means division.

When the X value is less than 1.80, it means that more and more ester polythiol compounds containing a thioester group represented by Formula 2 as a side reaction product increase. When the amount of the ester polythiol compound containing the thioester group of Formula 2 is increased, the effect of reducing the shrinkage when applied to an optical composition, increasing the adhesion between the substrate interface, and preventing the penetration of moisture or oxygen increases. Can be obtained.

However, in the case of extending the reaction time to increase the content of the ester polythiol compound containing the thioester functional group of Formula 2, the X value is not lower than 1.8, rather, a disulfide structure between thiol functional groups is generated, which is not desired. The structure of the polythiol dimer is created. This disulfide structure is a structure that is easily combined with oxygen (oxidized) and decomposed, which causes the color of polythiol to deteriorate.

On the other hand, when the X value exceeds 2.3, the content of the ester polythiol compound containing the thioester group of Formula 2 is insufficient, and thus it is difficult to expect the above-mentioned effects.

In one embodiment of the present invention, the following calculated using the SH value (g/eq.) α measured by wet titration for the composition for optical materials and the theoretically calculated SH value (g/eq.) β The P value of Equation 2 may be 1.03 to 1.07.

[Equation 2]

When the P value is less than 1.03, the content of the ester polythiol containing the thioester group of Formula 2 is small, so the shrinkage rate increases when added to the curable composition, so the adhesion to the substrate decreases, and the permeation of moisture or oxygen is convenient. If it exceeds 1.07, a disulfide structure between thiol functional groups is generated, which contains a lot of unwanted impurities of the polythiol dimer structure, resulting in poor liquid color and composition of the cured product. When added to, a problem of slowing curability may occur.

In addition, when the composition for an optical material is represented by an L*a*b* color system, the liquid b* may be 2.0 or less. When the b* exceeds 2.0, it means that the color of the liquid phase of the composition is opaque or yellow, and the color of the cured product using the composition is yellow or opaque, so it is not applicable to display materials that must be clear and transparent. Difficult problems can arise, which is not desirable.

In one embodiment of the present invention,

In Formula 1 and Formula 2,

A is pentaerythritol, a tetrahydric alcohol,

R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or a C1 to C5 alkyl group,

k is 0 or 1, o is 4 when k is 0, o is 3 when k is 1,

l is 0 or 1, when l is 0, p is 3 and q is 1, when l is 1, p is 2, and q is 1;

m and n may each independently be a natural number of 1 to 3.

Specifically, the compound of Formula 1 above includes the following Formula 5 and Formula 6, and the compound of Formula 2 may include the following Formula 7 and Formula 8.

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In the composition for an optical material of the present invention, the ester polythiol compound of Formula 1 includes a compound containing at least one hydroxyl group and a compound not containing a hydroxyl group,

The ester polythiol compound containing a thioester group of Formula 2 may include a compound containing one or more hydroxyl groups and a compound not containing a hydroxyl group.

Among the ester polythiol compounds of Formula 1, compounds that do not contain a hydroxyl group include ethylene glycol dimercaptoacetate, trimethylolpropane trimercaptoacetate, pentaerythritol tetramercaptoacetate, dipentaerythritol hexamercaptoacetate, and ethylene glycol di( 3-mercaptopropionate), trimethylolpropane tri(3-mercaptopropionate), pentaerythritol tetra (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate) ), ethoxylated trimethylolpropane tri(3-mercaptopropionate), tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, polycaprolactone tetra(3-mercaptopro) Cypionate), pentaerythritol tetra(3-mercaptobutylate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)- It may be one or more selected from the group consisting of 1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and trimethylolpropane tris (3-mercaptobutylate).

The composition for an optical material of the present invention is based on 1 equivalent of thiol contained in the ester polythiol compound of Formula 1 and the ester polythiol compound including the thioester functional group of Formula 2,

An active energy ray-curable compound having an unsaturated double bond containing 0.8 to 20.0 equivalents of an ethylenically unsaturated double bond;

An epoxy compound containing 0.8 to 20.0 equivalents of an epoxy group; And

An isocyanate compound containing 0.8 to 1.2 equivalents of an isocyanate group; It may further include one or more selected from among.

In the case where the active energy ray-curable compound having an unsaturated double bond is included, a photoinitiator is further included;

When the epoxy compound is included, at least one selected from an amine curing agent, an acid anhydride curing agent, an amine-based curing accelerator, and a phosphorus curing accelerator is further included;

When the isocyanate compound is included, at least one selected from a tin-based reaction catalyst and an amine-based reaction catalyst may be further included.

An active energy ray-curable compound having an unsaturated double bond and a photoinitiator; Epoxy compounds, amine curing agents, acid anhydride curing agents, amine curing accelerators, and phosphorus curing accelerators; And an isocyanate compound, a tin-based reaction catalyst, and an amine-based reaction catalyst; components known in the art may be used without limitation.

The composition for an optical material including the ester polythiol mixture can be applied to various fields. For example, it can be used as a thio-ene composition for photocuring, a thio urethane-based casting molding composition, and a curing agent for an epoxy curing system.

The photocurable thio-ene composition is a mixture of vinyl, aryl, (meth)acrylic compounds and the ester polythiol compound to prevent penetration of oxygen, thereby increasing curing efficiency, reducing shrinkage, and metal substrates or crystalline polymer substrates. You can increase the adhesion. In addition, due to the hydrophobic properties of the ester polythiol, there are several advantages that can lower moisture penetration. The photocurable thio-ene composition is 0.8 to ethylenically unsaturated double bonds based on 1 equivalent of thiol contained in the ester polythiol compound and the ester polythiol compound containing a thioester functional group in the composition for optical materials. Mix 20.0 equivalents and additionally contain a photoinitiator. The active energy ray-curable compound having an ethylenically unsaturated double bond is irrelevant as long as it is a compound having a double bond, but a (meth)acrylate type is preferable. The (meth) acrylate oligomer and/or monomer may be included. The photocurable (meth)acrylate oligomer may be used to control the mechanical properties and curing shrinkage of the cured product, examples of which include epoxy (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate , Melamine (meth) acrylate, phosphoric acid (meth) acrylate, silicone (meth) acrylate, and the like can be used. The monomer having the (meth)acryloyl group lowers the viscosity of the mixture and affects the appearance and physical properties after curing, so it can be appropriately selected and used according to the purpose. Examples thereof include neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, 1,2,4-cyclohexanetetra (meth) )Acrylate, pentaglycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate , Dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol hexa(meth)acrylate, bis(2-hydroxyethyl)iso Cyanurate di (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isooctyl (meth) acrylate, isodexyl (meth) It may be selected from the group consisting of acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, and isoborneol (meth) acrylate. .

The photoinitiator may be used without limitation as long as it is used in the art. Specifically, 2-methyl-1-[4-(methylthio)phenyl]2-morpholinepropanone-1, diphenylketone benzyldimethylketal, 2-hydroxy-2-methyl-1-phenyl-1-one , 4-hydroxycyclophenylketone, dimethoxy-2-phenylacetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4-chloroacetophenone, 4,4-dimethoxyaceto Phenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexylphenylketone, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, bis-(2,6-dimethoxybenzoyl)-2, At least one selected from the group consisting of 4,4-tri methyl pentyl phosphine oxide and benzophenone may be used. The substrate used in the photocuring thio-ene composition is a non-organic substrate such as glass and metal, polyethylene telephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), polyethylene (PE ), polypropylene (PP), polyimide (PI), polyamide (PA), and other crystalline/amorphous polymer substrates, especially crystalline polymer substrates that are not treated with organic polymer primers, or metal oxides. It has excellent adhesion to the polymer substrate on the surface of the deposited metal. In addition, the photocuring thio-ene composition has a low shrinkage and can be applied as an inkjet material for 3D printing.

The thiourethane-based casting molding composition includes 0.8 to 1.2 equivalents of isocyanate, polymerizable catalyst, and internal mold release agent based on 1 equivalent of thiol contained in the ester polythiol compound and the ester polythiol compound containing a thioester functional group in the composition for optical materials. It is possible to prepare a mixture for casting molding with a composition comprising a. The isocyanate compound is not particularly limited as long as it is a polyisocyanate compound having at least two or more isocyanate groups in one molecule. Specifically, hexamethylene diisocyanate, 1,5-pentane diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, 1,3-butadiene-1,4- Diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecan triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanato Methyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, lysine diisocyanatomethyl ester, lysine triisocyanate, 1,2-diisothiocyanatoethane, 1,6-diisothio Cyanatohexane, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexanediisocyanate, dicyclohexyldimethylmethane isocyanate, 2,5-bis( Isocyanatomethyl)-bicyclo[2.2.1]heptane, 2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 3,8-bis(isocyanatomethyl)tricyclodecane , 3,9-bis(isocyanatomethyl)tricyclodecane, 4,8-bis(isocyanatomethyl)tricyclodecane, 4,9-bis(isocyanatomethyl)tricyclodecane, bis(4- Aliphatic polyisocyanate compounds such as isocyanatocyclohexyl)methane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, and cyclohexanediisothiocyanate; 1,2-diisocyanatobenzene, 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, tolylene diisocyanate, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, ethyl Phenylene diisocyanate, isopropyl phenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylenediisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, biphenyl diisocyanate, toluene diisocyanate, toluidine diisocyanate 4,4'-methylenebis(phenylisocyanate), 4,4'-methylenebis(2-methylphenylisocyanate), dibenzyl-4,4'-diisocyanate, bis(isocyanatophenyl)ethylene, bis(isocyanate) Nattomethyl)benzene, m-xylylenediisocyanate, bis(isocyanatoethyl)benzene, bis(isocyanatopropyl)benzene, α,α,α',α'-tetramethylxylylenediisocyanate, bis(iso Cyanatobutyl)benzene, bis(isocyanatomethyl)naphthalene, bis(isocyanatomethylphenyl)ether, bis(isocyanatoethyl)phthalate, 2,5-di(isocyanatomethyl)furan, 1,2- Diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2,5-diisothiocyanato- m-xylene, 4,4'-methylenebis(phenylisothiocyanate), 4,4'-methylenebis(2-methylphenylisothiocyanate), 4,4'-methylenebis(3-methylphenylisothiocyanate) Acid), 4,4'-diisothiocyanatobenzophenone, 4,4'-diisothiocyanato-3,3'-dimethylbenzophenone, bis(4-isothiocyanatophenyl) ether, etc. Polyisothiocyanate compounds; Bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatomethyl) sulfone, bis (Isocyanatomethyl) disulfide, bis (isocyanatoethyl) disulfide, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (Isocyanatomethylthio)ethane, bis(isocyanatoethylthio)ethane, 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane, 1,2,3-tris (isocyanato Methylthio)propane, 1,2,3-tris(isocyanatoethylthio)propane, 3,5-dithia-1,2,6,7-heptanetetraisocyanate, 2,6-diisocyanatomethyl-3 ,5-dithia-1,7-heptanediisocyanate, 2,5-diisocyanate methylthiophene, 4-isocyanatoethylthio-2,6-dithia-1,8-octane diisocyanate, thiobis( 3-isothiocyanatopropane), thiobis (2-isothiocyanatoethane), dithiobis (2-isothiocyanatoethane), 2,5-diisocyanatotetrahydrothiophene, 2,5-di Socyanatomethyltetrahydrothiophene, 3,4-diisocinatomethyltetrahydrothiophene, 2,5-diisocyanato-1,4-ditian, 2,5-diisocyanatomethyl-1,4-dithione An, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis(isocyanatomethyl)-1,3-dithiolane, 4,5-diisocyanatomethyl-2-methyl-1 Sulfur-containing aliphatic polyisocyanate compounds such as ,3-dithiolane; Aromatic sulfide-based polyisocyanate compounds such as 2-isocyanatophenyl-4-isocyanatophenyl sulfide, bis(4-isocyanatophenyl)sulfide, and bis(4-isocyanatomethylphenyl)sulfide; Bis(4-isocyanatophenyl)disulfide, bis(2-methyl-5-isocyanatophenyl)disulfide, bis(3-methyl-5-isocyanatophenyl)disulfide, bis(3-methyl- Aromatic disulfide polyisocyanates such as 6-isocyanatophenyl) disulfide, bis(4-methyl-5-isocyanatophenyl) disulfide, and bis(4-methoxy-3-isocyanatophenyl) disulfide And compounds. More specifically, the polyisocyanate compound may be 1,3-bis(isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, isophorone diisocyanate, m-xylylene diisocyanate, toluene diisocyanate, or a mixture thereof. . Examples of the internal mold release agent include fluorine-based nonionic surfactants having a perfluoroalkyl group, a hydroxyalkyl group, or a phosphate ester group; Silicone-based nonionic surfactants having a dimethylpolysiloxane group, a hydroxyalkyl group or a phosphate ester group; Alkyl quaternary ammonium salts such as trimethylcetyl ammonium salt, trimethylstearyl, dimethylethylcetyl ammonium salt, triethyldodecyl ammonium salt, trioctylmethyl ammonium salt, diethylcyclohexadodecyl ammonium salt, etc.; And components selected from among acidic phosphate esters may be used alone or in combination of two or more. The polymerization catalyst may be used regardless of a catalyst capable of activating the polymerization of thiol and isocyanate. In general, a tin (tin)-based catalyst and an amine-based catalyst are used, and a halogenated tin polymerization catalyst such as dibutyltin dichloride or dimethyltin dichloride may be used.

As a curing agent for the epoxy curing system, a polythiol contained in an ester polythiol compound and an ester polythiol compound containing a thioester functional group may be used. The epoxy resin composition prepared by using polythiol as a curing agent and including tertiary amines, phosphines, phosphonium salts, quaternary ammonium salts, etc. as a curing accelerator is a low-temperature fast-curing epoxy resin composition that can be cured at room temperature It is known as, and can be applied to (instantaneous) adhesives, sealants, molds, and the like. In addition, a boric acid ester compound and a solid latent curing agent may be mixed to secure curing speed and stability. Any epoxy resin can be used as long as it has two or more epoxy groups per molecule on average. Specific examples include polyglycidyl ether obtained by reacting a polyhydric phenol such as bisphenol A, bisphenol F, bisphenol AD, catechol, and resorcinol, or a polyhydric alcohol such as glycerin and polyethylene glycol with epichlorohydrin; glycidyl ether esters obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; Polyglycidyl ester obtained by reacting a polycarboxylic acid such as phthalic acid and terephthalic acid with epichlorohydrin; And epoxidized phenol novolak resins, epoxidized cresol novolac resins, epoxidized polyolefins, alicyclic epoxy resins, and other urethane-modified epoxy resins. Curing accelerators, boric acid ester compounds, solid latent curing agents, and the like can be found in known literature. The epoxy resin composition is used by mixing 0.8 to 20.0 equivalents of an epoxy functional group with respect to 1 equivalent of thiols contained in the ester polythiol compound and the ester polythiol compound containing a thioester functional group included in the composition for optical materials, and this content The ratio can be adjusted depending on the application and curing process.

The present invention also,

A method of preparing a compound represented by Formula 1 and a compound represented by Formula 2 in one step by a condensation ester reaction of a compound represented by the following Formula 3 and a compound represented by Formula 4,

An ester polythiol mixture, characterized in that the water produced by condensation is removed using an azeotropic distillation method, but a process of continuously inducing a positive reaction by removing 95 to 110% of water of the theoretical dehydration amount to the outside by dehydrating it. Regarding the manufacturing method of:

[Formula 3]

[Formula 4]

In Chemical Formula 3 and Chemical Formula 4

A is each independently C1 ~ C12 aliphatic hydrocarbon group,

R ₁ and R ₂ are each independently hydrogen or a C1 to C5 alkyl group,

K is a natural number from 2 to 6,

m is a natural number from 1 to 5,

The alkylene groups represented by m may be substituted or unsubstituted with C1 to C5.

When removing the water produced by condensation in the above using an azeotropic distillation method, it is more preferable to remove water in an amount of 95 to 110% of the theoretical dehydration to the outside by dehydrating it.

In the case of dehydrating water less than 95% of the theoretical dehydration amount to the outside, unreacted hydroxyl groups are relatively large, and the condensation ester reaction does not proceed to overreaction. Therefore, the thiol functional group of the prepared ester polythiol compound is unreacted. It is difficult to obtain an ester polythiol compound containing a thioester functional group of Formula 2 because the side reaction of the carboxylic acid of the captoalkyl carboxylic acid does not occur easily. In addition, if the reaction is overreacted to exceed 110%, the amount of dehydration does not increase further, and disulfide that reacts with the thiol groups at the ends is produced, which causes a problem in the curing reaction, which increases the SH value of the wet titration method. It can be confirmed that a large amount of impurity peaks that cannot be identified even on the high-speed chromatography (HPLC) analysis peak can be expected. In addition, since the disulfide is easily oxidized by reacting with oxygen, the ester polythiol color changes to yellow or red, which is not preferable.

The preparation method may be carried out by reacting 1.01 to 1.10 equivalents of carboxyl groups contained in the compound of Formula 4 based on 1 equivalent of hydroxyl groups contained in the compound of Formula 3 above.

In the case where the carboxyl group contained in the compound of Formula 4 is reacted with less than 1 equivalent, the amount of the condensation ester reaction proceeding to the overreaction is relatively low, and thus the unreacted mercapto alkyl with the thiol functional group of the prepared ester polythiol compound Since the amount of the side-reactant of the carboxylic acid may be relatively small, it is difficult to obtain a sufficient amount of the ester polythiol compound containing the thioester functional group of Formula 2. In addition, when the amount exceeds 1.10 equivalents, the amount of condensation ester reaction proceeds as overreaction, and the amount of side-reactants of the unreacted mercapto alkyl carboxylic acid with the thiol functional group of the prepared ester polythiol compound will be relatively large. It is possible to obtain a sufficient amount of the ester polythiol compound containing the thioester functional group of Formula 2, but the mercapto alkyl carboxylic acid is discarded in the subsequent purification process without being reacted with the reacted mercapto alkyl carboxylic acid It is not preferable because the amount of is increased, the manufacturing cost is increased, and the amount of disulfide produced by the excess mercapto alkyl carboxylic acid increases, causing color problems.

The preparation method can be represented, for example, by the following Schemes 1 and 2:

[Scheme 1]

[Scheme 2]

The reaction between the thiol group and the carboxylic acid shown in Reaction Scheme 2 is less reactive than the reaction between the alcohol and carboxylic acid shown in Reaction Scheme 1, so it cannot be called the main reaction, but at the end of the ester polythiol production process, a large amount of hydroxyl groups are mostly exhausted. Therefore, the possibility that the remaining amount of the mercapto alkyl carboxylic acid can react with the thiol functional group increases.

The bifunctional or higher alcohol (1-1) forms an ester polythiol compound (1-3) through an ester condensation reaction with a mercapto alkyl carboxylic acid compound (1-2). As the bifunctional or higher alcohol (1-1), for example, one selected from C2 to C12 alkylene glycol, diethylene glycol, glycerol, dipropylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. Alternatively, two or more types may be used.

The alkylene glycol is one or two or more selected from ethylene glycol, trimethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, and tetramethylene glycol. Can be used.

As the mercapto alkyl carboxylic acid compound (1-2), for example, thioglycolic acid, 3-mercaptopropionic acid, 2-mercaptopropionic acid, 3-mercaptobutyl acid, 2-mercaptoisobutyl acid, And one or two or more selected from 3-mercaptoisobutyl acid and the like may be used.

The ester condensation reaction may continuously induce a forward reaction by removing the generated water to the outside using an azeotropic distillation method.

If the above reaction is described in detail, esterification by azeotropic distillation by gradually increasing the temperature of a bifunctional or higher polyhydric alcohol (1-1) and mercapto alkyl carboxylic acid (1-2) in an organic solvent to the boiling point of the organic solvent in the presence of a catalyst. The reaction can be carried out. In this case, the reaction temperature may be determined by the boiling point of the solvent, and may be 60 to 130°C. The mercapto alkyl carboxylic acid compound (1-2) may be used in an excessive amount based on 1 equivalent of hydroxyl groups contained in the bifunctional or higher polyhydric alcohol, and specifically, 1.01 to 1.10 equivalents may be used. As a catalyst during the reaction, a sulfonic acid series such as paratoluenesulfonic acid, sulfuric acid, benzenesulfonic acid, naphthalenesulfonic acid, fluorosulfonic acid, and chlorosulfonic acid may be used. As the organic solvent, it is preferable to use an organic solvent having a boiling point of 60 to 130°C, capable of azeotropic distillation with water and not undergoing transesterification reaction.For example, organic solvents such as toluene, xylene, benzene, hexane, and heptane A solvent can be used. When the boiling point of the organic solvent is lower than 60° C., the reaction may be difficult to proceed, and when it is higher than 130° C., disulfide is formed by reaction between thiols, and the viscosity and molecular weight of the synthesized compound may rapidly increase.

In order to proceed with the reaction of [Scheme 2], water of 95% to 110% of the theoretical dehydration amount may be dehydrated to the outside. In addition, in order to effectively discharge water as a by-product to the outside, an inert gas such as nitrogen is sufficiently introduced to facilitate azeotropic distillation. In addition, by raising the temperature of the fruit to a temperature 10℃, preferably 20℃ higher than the boiling point of the aliphatic or aromatic solvent used for azeotropic distillation, azeotropic distillation is rapidly proceeded to effectively release the dehydrated material to the outside. Can promote. Compounds produced by the side reaction according to [Scheme 2] include, for example, compounds of the following Chemical Formulas 7 and 8. The compound of Formula 8 below is a compound produced by a side reaction of [Scheme 2] with an ester polythiol compound (1-3) having an unreacted hydroxyl group due to structural granulation disorder.

[Formula 7]

[Formula 8]

The present invention also,

A 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 relates to a quantum dot film, characterized in that formed by the composition for an optical material of the present invention including quantum dots.

The curing process of the quantum dot film is preferably a curing process by light having a high curing speed in terms of productivity, but is not limited thereto. Specifically, the curing may be performed using, without limitation, a process of curing by light, a process of curing by mixing two methods of light and heat, a process of curing by heat alone, and the like.

As the first barrier layer and the second barrier layer, a film in which a metal oxide-based component is deposited on a transparent crystalline polymer substrate with little penetration of moisture or oxygen may be used, and preferably, transparent polyethylene telephthalate (PET) Products with alkylsilane deposited on the film are good. The quantum dot particles include a core layer and a shell layer positioned 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 is III- It may be used that includes a group V compound, but is not limited thereto.

Examples of the group III-V compound of the core layer include a binary compound selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; A ternary compound 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 GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, GaAlNP, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and a quaternary compound selected from the group consisting of a mixture thereof.

The core layer preferably includes In and P, and the shell layer includes at least one of Zn, Se and S, and may further include a non-polar ligand having 5 to 30 carbon atoms.

The scattering particles (E) are silica (Silica), alumina (Alumina), silicon (Silicon), alumina (Alumina), titanium dioxide (TiO ₂ ), zirconia (ZrO ₂ ), barium sulfate (Barium Sulfate), zinc oxide ( ZnO), poly(methylmethacrylate), PMMA), and may be one or more selected from the group consisting of benzoguanamine-based polymers. In addition, those having an average particle diameter of 10 to 100 nanometers may be preferably used.

The quantum dot film may be disposed on a path of emission light of a blue LED emitting light having a dominant wavelength in the range of 440 nm to 460 nm, and the quantum dot particles in the quantum dot film convert at least some wavelengths of the emission light into green light. The first quantum dot particles and the second quantum dot particles that convert at least some wavelengths of the emitted light into red light may be included, but are not limited thereto.

In addition, the present invention

It relates to a backlight unit including the quantum dot film of the present invention and a liquid crystal display device including the backlight unit.

In the quantum dot film, the backlight unit, and the liquid crystal display, for other configurations other than the configuration including the quantum dot layer formed of the composition for an optical material of the present invention including quantum dots and a quantum dot film including the same, techniques known in the art It can be used without this limitation.

Hereinafter, preferred embodiments are presented to aid in the understanding of the present invention, but the following examples are only illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It is natural that such changes and modifications fall within the scope of the appended claims.

Test Example 1: The following Formula 1 and Formula 2 compounds and containing them Measurement of properties of ester polythiol mixture

(1) High performance liquid chromatography measurement

Shimadzu LC-20AT was used, and two columns were connected to Acclaim 120 C18 (filled silica particle size 5㎛, pore 120ÅA, column size 4.6×250mm). The mobile phase started with acetonitrile and 0.01M potassium phosphate aqueous solution at a ratio of 4/6 and finally terminated with acetotrile alone to improve the resolution through a concentration gradient. The measurement wavelength was 230 nm, the flow rate was 1.0 ml/min, the injection amount was 20 μl, and the sample was pretreated by mixing 10 g of acetonitrile with 0.16 g of the sample.

(2) SH value measurement

After putting about 0.1 g of the prepared ester polythiol mixture in a beaker, 50 mL of chloroform was added and stirred for 10 minutes, and then 10 mL of isopropyl alcohol was added, followed by stirring for 10 minutes. The solution was titrated using a 0.05 N iodine standard solution (Wako), and the SH value (g/eq.) α was calculated by applying to Equation 2 below.

[Equation 2]

α = (sample weight (g))/(0.05 × amount of iodine consumed (L) × factor of iodine solution)

(3) Calculation of theoretical SH value

The theoretical SH value (g/eq.) can be represented by the β value of Equation 3 below.

[Equation 3]

β = (theoretical molecular weight of ester thiol)/(theoretical functional group number of ester thiol)

In the above, the theoretical molecular weight and the number of theoretical functional groups of the ester thiol are determined by the structure of the compound of Formula 1 that does not contain an unreacted hydroxyl group.

(4) P value calculation

Using the values calculated in Equations 2 and 3, the P value may be calculated by Equation 4 below.

[Equation 4]

P = α/β

The P value cannot be less than 1, and the closer the P value is to 1, the higher the purity.

(5) b* measurement

The mixture was injected into a quartz cell having an inner thickness of 10 m, and b* was calculated using a color difference meter (CM-3700A, Minolta). As the b* value is smaller, it can be determined that the color of the liquid is colorless and transparent.

Synthesis Example 1: Including the compounds of formula 1 and formula 2 Preparation of ester polythiol mixture

In a 4-neck 2L double jacket reactor equipped with a thermometer, mechanical stirrer, Deanstock, and nitrogen inlet tube, 113.7 g (0.84 mol) of pentaerythritol and 392.3 g (3.70 of 3-mercaptopropionic acid) and 3-mercaptopropionic acid so that the equivalent ratio of carboxyl groups to hydroxyl groups is 1.10. Mol), 1.6 g of paratoluene sulfonic acid, and 669.6 g of toluene were added. At this time, the temperature of the heat medium connected to the double jacket reactor was maintained at 140°C, and toluene was azeotropically distilled while nitrogen was introduced to remove water generated as a by-product to the outside. At this time, the temperature inside the reactor was maintained at 110±5°C. The reaction was further carried out for 2 hours at the dehydration amount of water 61.7g (102.6% obtained compared to the theoretical value of 60.1g), but no more water came out. At this time, the reaction was terminated, and the reactant and 410 g of 10% sodium carbonate aqueous solution were added to a separatory funnel to remove the catalyst and unreacted 3-mercaptopropionic acid, and washed three times with 410 g of distilled water.

Thereafter, toluene and a trace amount of water were completely removed through a heating and decompression process, and then filtered through a 1 μm Teflon filter to prepare 381 g of an ester polythiol mixture (yield 95.2%).

_{^{13 C-NMR -CH 2 -SH 19.6ppm}} , -CH 2 - 33.8ppm, -C- 37.9ppm, -CH 2 -O- 62.4ppm

-CH ₂ -OH 64.9ppm, -O-(C=O)- 171.1ppm, -S-(C=O)- 199.3ppm

FT-IR ether stretch 1100cm ^-1 , ester stretch 1760cm ^-1 , thiol stretch 2451cm ^-1

b* 0.62

SH value α= 126.43g/eq.(measured value), β=488.64/4=122.16 g/eq.(theoretical value)

HPLC (high-speed liquid chromatography) measurements (Table 1)

Formula 1 compound (including 1 unreacted OH group) Compound of Formula 2 (including 1 unreacted OH group) Compound of formula 1 (without unreacted OH group) Compound 2 (without unreacted OH group) Retention Time(min.) 17.7 20.8 23.8 25.8 Area 2,220,379 971,355 12,785,224 6,278,718 Area% 9.98% 4.36% 57.45% 28.21% m/z (mass value) 400.06789 488.06595 488.06637 576.06441

Synthesis Example 2: Including the compounds of formula 1 and formula 2 Preparation of ester polythiol mixture

The reaction was carried out in the same manner as in Synthesis Example 1 except that 128.5 g (0.94 mol) of pentaerythritol, 356.3 g (3.86 mol) of thioglycolic acid, and 1.8 g of paratoluene sulfonic acid were used so that the equivalent ratio of the carboxyl group to the hydroxyl group was 1.03. I did. The reaction proceeded for an additional 2 hours at 66.3 g of dehydration amount of water (97.6% of the theoretical dehydration amount of 67.9 g was obtained), but no more water was dehydrated, and the reaction was terminated at this time. It was 387 g (yield 96.8%) of an ester polythiol mixture obtained through a purification process and a solvent removal process.

¹³ C-NMR -CH ₂ -SH 26.5ppm, -C- 37.9ppm, -CH ₂ -O- 61.7ppm

-CH ₂ -OH 64.9ppm, -O-(C=O)- 170.7ppm, -S-(C=O)- 196.5ppm

FT-IR ether stretch 1100cm ^-1 , ester stretch 1760cm ^-1 , thiol stretch 2451cm ^-1

b* 0.53

SH value α = 113.87g/eq.(measured value) β=432.54/4=108.14 g/eq.(theoretical value)

HPLC (high-speed liquid chromatography) measurements (Table 2)

Formula 1 compound (including 1 unreacted OH group) Compound of Formula 2 (including 1 unreacted OH group) Compound of formula 1 (without unreacted OH group) Compound 2 (without unreacted OH group) Retention Time(min.) 14.1 16.3 19.9 21.4 Area 6,361,717 2,705,246 22,712,422 10,554,689 Area% 15.03% 6.39% 53.65% 24.93% m/z (mass value) 358.02136 432.00356 432.00398 505.98624

Synthesis Example 3: Including compounds of Formula 1 and Formula 2 Preparation of ester polythiol mixture

The reaction was carried out in the same manner as in Synthesis Example 1 except that 365.5 g (3.44 mol) of 3-mercaptopropionic acid was used so that the equivalent ratio of the carboxyl group to the hydroxyl group was 1.03, and the dehydration amount of water was 65.9 g (109.7% compared to the theoretical value 60.1 g). Obtained) was maintained for 10 hours, at this time, the total amount of dehydration of water was 66.2 g (110.2% compared to the theoretical value of 60.1 g), the water was no longer dehydrated, the reaction was terminated. 343 g of an ester polythiol mixture (yield 85.3%) obtained through the purification process and the solvent removal process was prepared.

_{^{13C -NMR -CH 2 -SH 19.6ppm, -CH}} 2 - 33.8ppm, -C- 37.9ppm, -CH 2 -O- 62.4ppm

-CH ₂ -OH 64.9ppm, -O-(C=O)- 171.1ppm, -S-(C=O)- 199.3ppm

FT-IR ether stretch 1100cm ^-1 , ester stretch 1760cm ^-1 , thiol stretch 2451cm ^-1

b* 3.24

SH value α = 132.17g/eq.(measured value) β=488.64/4=122.16 g/eq.(theoretical value)

HPLC (high-speed liquid chromatography) measurements (Table 3)

Formula 1 compound (including 1 unreacted OH group) Compound of Formula 2 (including 1 unreacted OH group) Compound of formula 1 (without unreacted OH group) Compound 2 (without unreacted OH group) Retention Time(min.) 17.7 20.8 23.8 25.8 Area 2,083,947 1,017,676 11,913,553 6,273,530 Area% 9.79% 4.78% 55.96% 29.47% m/z (mass value) 400.06789 488.06595 488.06637 576.06441

Synthesis Example 4: Including compounds of Formula 1 and Formula 2 Synthesis of ester polythiol mixture

The reaction was carried out in the same manner as in Synthesis Example 2, except that 397.9 g (4.32 mol) of thioglycolic acid was used so that the equivalent ratio of the carboxyl group to the hydroxyl group was 1.15, and the amount of water dehydration was 63.3 g (93.2% compared to the theoretical value 67.9 g). At the end of the reaction, 331 g (yield 82.8%) of an ester polythiol mixture obtained through a purification process and a solvent removal process was prepared.

C-NMR -CH ₂ -SH 26.5ppm, -C- 37.9ppm, -CH ₂ -O- 61.7ppm

-CH ₂ -OH 64.9ppm, -O-(C=O)- 170.7ppm, -S-(C=O)- 196.5ppm

FT-IR ether stretch 1100cm ^-1 , ester stretch 1760cm ^-1 , thiol stretch 2451cm ^-1

b* 0.49

SH value α= 109.21 g/eq. (measured value) β= 432.54/4 = 108.14 g/eq. (theoretical value)

HPLC (high-speed liquid chromatography) measurements (Table 4)

Formula 1 compound (including 1 unreacted OH group) Compound of Formula 2 (including 1 unreacted OH group) Compound of formula 1 (without unreacted OH group) Compound 2 (without unreacted OH group) Retention Time(min.) 14.1 16.3 19.9 21.4 Area 5,278,740 809,094 29,593,476 5,410,282 Area% 12.85% 1.97% 72.02% 13.17% m/z (mass value) 358.02136 432.00356 432.00398 505.98624

Preparation Example 1: Synthesis of quantum dot particles

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 converted 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 quickly cooled to room temperature, and the precipitate obtained by centrifugation was dispersed in toluene. In the obtained InP semiconductor nanocrystal, the particle size was determined according to the reaction time, and the maximum UV wavelength was 420 to 600 nm according to the particle size. Zinc acetate (zinc acetate) 0.3 mmoL (0.056g), oleic acid (oleic acid) 0.6 mmol (0.189g), and trioctylamine (trioctylamine) 10 mL was added to the reaction flask was vacuum-treated at 120 ℃ 10 minutes. After replacing the inside of the reaction flask with N ₂ , the temperature was raised to 220°C. Toluene dispersion (OD: 0.15) and TOPS 0.6 mmol (sulfur dispersed/dissolved in trioctylphosphine) prepared above of the InP semiconductor nanocrystals prepared above were added to the reaction flask and heated to 280° C. and reacted for 30 minutes. After completion of the reaction, 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 reactant 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 the UV-vis absorption spectrum to confirm red or green emission. In the above method, a dispersion of quantum dot particles emitting red light or green light was prepared.

Example 1: Preparation of a composition for an optical material

40 parts by weight of the ester polythiol mixture of Synthesis Example 1, 60 parts by weight of trimethylolpropane triacrylate (M300 from Miwon Specialty Chemical), 0.3 parts by weight of red light-emitting particles among the quantum dot particles of Preparation Example 1, and 0.7 blue light-emitting particles 5 parts by weight of zinc oxide as a scattering agent (FINEX 30 from Sakai Chemical, average particle diameter 35 nm), 3 parts by weight of 2,4,6-tribenzoyldiphenylphosphine oxide (Darocure TPO from IGM) as a photoinitiator. The mixture was uniformly mixed at a speed of 500 rpm through a stirrer.

Example 2: Preparation of composition for optical material

A composition was prepared in the same manner as in Example 1, except that 40 parts by weight of the ester polythiol mixture of Synthesis Example 2 was added.

Example 3: Preparation of composition for optical material

A composition was prepared in the same manner as in Example 1, except that 20 parts by weight of the ester polythiol mixture of Synthesis Example 1 and 80 parts by weight of trimethylolpropane triacrylate (Miwon Specialty Chemical Co., Ltd. M300) were added.

Example 4: Preparation of composition for optical material

A composition was prepared in the same manner as in Example 1, except that 20 parts by weight of the ester polythiol mixture of Synthesis Example 2 and 80 parts by weight of trimethylolpropane triacrylate (Miwon Specialty Chemical M300) were added.

Comparative Example 1: Preparation of composition for optical material

A composition was prepared in the same manner as in Example 1, except that 40 parts by weight of the ester polythiol mixture of Synthesis Example 3 was added.

Comparative Example 2: Preparation of composition for optical material

A composition was prepared in the same manner as in Example 1, except that 40 parts by weight of the ester polythiol mixture of Synthesis Example 4 was added.

Examples 5 to 8 and Comparative Examples 3 to 4: Preparation of quantum dot film

For the first film and the second film, a polyethylene terephthalate film (Toyobo A4300) having a thickness of 50 μm was used. The binder resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 2 were filtered through a filter made of 0.2 μm Teflon, and then reduced pressure for 30 minutes to completely remove air bubbles in the binder resin composition. The binder resin composition was coated on the first film by using a micro bar, and the second film was laminated on the second film using a rubber roll so as not to generate bubbles, thereby performing ultraviolet curing. At this time, the UV curing device used a Litgen UV curing machine (UVMH1001) equipped with a metal halide lamp, and the amount of light in the UVA region measured using the EIT's UV Puck II was 1500 mJ. The thickness of the cured binder resin composition was maintained at 50±2 μm.

Test Example 2: Evaluation of physical properties of quantum dot film

The physical properties of the quantum dot film prepared above were evaluated, and the results are shown in Tables 3 and 4 below.

1) O ₂ Transmittance (cc/m/day/atm)

Measurements were made using a Mocon OX-TRAN Model 2/21 apparatus (Mocon, Inc., Minneapolis, MN). ASTM Method D3985 (January 30, 1981 Standard of oxygen gas permeability through plastic film and sheeting using a Coulometric Sensor) using test gases of 3% O ₂ and 97% N ₂ at 23 °C Test method).

2) Measurement of moisture permeability

The moisture permeability of the quantum dot film was measured using a moisture permeability meter (MOCON, AQUATRAN MODEL 2).

3) luminance measurement

After cutting the quantum dot film to fit A4 size, the backlight of the Samsung SUHD TV JS6500 model

After the power was applied by installing it in the center of the panel, the luminance (Y) of 13 points was measured using a luminance meter (CS-2000, Minolta) to obtain an average value. Compared to the initial luminance, the luminance (Y) and the rate of change (Y (%)) compared to the initial luminance were measured after leaving heat resistance (80°C) and high temperature and high humidity (90°C, 60%) for 250 hours.

4) Edge discoloration

After cutting the quantum dot film to fit A4 size, leave the film at 85℃ and 85% humidity for 48 hours, attach it to the center of the backlight of the Samsung SUHD TV JS6500 model, apply power, and see if there is any color loss in each corner Visually, if there is no color loss, ◎, if there is a slight color loss, ○, if there is obvious color loss on two or more of the slopes, △, and if there is obvious color loss on three or more of the slopes, it is marked with X.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Oxygen permeability
(cc/m/day/atm) 0.021
±0.002 0.020
±0.002 0.024
±0.002 0.024
±0.002 0.031
±0.003 0.029
±0.003 Moisture permeability(g/m ² ·day) <0.8 <0.8 1.8 2.1 1.6 4.7 Film yi 1.2 1.3 2.0 1.9 4.9 2.8 Initial luminance, Y(cd/m ² ) 587.3 585.9 579.6 581.3 582.1 586.2 High temperature luminance
(Y(%)) 581.1
(98.9) 583.6
(99.6) 561.3
(96.8) 563.1
(96.9) 521.7
(89.6) 508.7
(86.8) High temperature and high humidity
(Y(%)) 523.4
(89.1) 552.6
(89.2) 511.3
(88.2) 509.6
(87.7) 462.8
(79.5) 431.6
(73.6) Edge discoloration ◎ ◎ ○ ○ △ X

As can be seen from Table 5, the quantum dot film (Examples 5 to 8) prepared using the composition for an optical material of the present invention is a quantum dot film prepared using the composition for an optical material of Comparative Example (Comparative Examples 3 to 4 ), the physical properties for oxygen permeability and moisture permeability were excellent, the luminance in high temperature and high temperature & high humidity environments was remarkably excellent, and it was confirmed to be very excellent in edge bleaching characteristics.

Claims (13)

An ester polythiol compound represented by the following formula (1), and
As a composition for an optical material comprising an ester polythiol compound containing a thioester functional group represented by the following formula (2),
The composition for an optical material has a P value of 1.03 to 1.07 calculated by using the SH value (g/eq.) α measured by wet titration and the theoretically calculated SH value (g/eq.) β. Composition for an optical material, characterized in that:
[Equation 2]

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,
A is a C1 ~ C12 aliphatic hydrocarbon group, each independently containing or not containing an unsaturated group, of a linear, branched or cyclic, hetero group,
R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or a C1 to C5 alkyl group,
k and l are each independently an integer of 0 to 3,
o is a natural number from 2 to 6, p is a natural number from 0 to 5, q is a natural number from 1 to 6, p+q = a natural number from 2 to 6,
m and n are each independently a natural number of 1 to 5,
The alkylene groups represented by m and n may be substituted or unsubstituted with C1 to C5. The method of claim 1,
When the composition for an optical material is analyzed by high-speed liquid chromatography (HPLC), the peak area of the ester polythiol compound of Formula 1 and the thioester group of Formula 2 in the high-speed liquid chromatography (HPLC) spectrum The peak area of the thiol compound is a composition for an optical material, characterized in that the X value calculated by the following equation (1) satisfies 1.80 to 2.30:
[Equation 1]
X = Sum of the peak areas of the ester polythiol compound of Formula 1 / Sum of the peak areas of the ester polythiol compound containing the thioester group of Formula 2 The method of claim 1,
The composition for an optical material, wherein the composition for an optical material has a b* of 2.0 or less when expressed by an L*a*b* color system. The method of claim 1,
The compound of Formula 1 includes a compound of Formula 5 and a compound of Formula 6, wherein the compound of Formula 2 comprises a compound of Formula 7 and a compound of Formula 8 below:
[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or a C1 to C5 alkyl group;
m and n are each independently a natural number of 1 to 3. The method of claim 1,
The ester polythiol compound of Formula 1 includes a compound containing at least one hydroxyl group and a compound not containing a hydroxyl group,
The ester polythiol compound containing a thioester group of Formula 2 is a composition for an optical material comprising a compound containing at least one hydroxyl group and a compound not containing a hydroxyl group. The method of claim 5,
The composition for an optical material comprises 40 to 60% by weight of the compound of Formula 1 that does not contain a hydroxyl group. The method of claim 5,
Among the ester polythiol compounds of Formula 1, compounds that do not contain a hydroxyl group include ethylene glycol dimercaptoacetate, trimethylolpropane trimercaptoacetate, pentaerythritol tetramercaptoacetate, dipentaerythritol hexamercaptoacetate, and ethylene glycol di( 3-mercaptopropionate), trimethylolpropane tri(3-mercaptopropionate), pentaerythritol tetra (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate) ), ethoxylated trimethylolpropane tri(3-mercaptopropionate), tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, polycaprolactone tetra(3-mercaptopro) Cypionate), pentaerythritol tetra(3-mercaptobutylate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)- It is characterized in that at least one selected from the group consisting of 1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and trimethylolpropanetris (3-mercaptobutylate) A composition for an optical material. The method of claim 1,
The composition for an optical material is based on 1 equivalent of thiol contained in the ester polythiol compound of Formula 1 and the ester polythiol compound including the thioester group of Formula 2,
An active energy ray-curable compound having an unsaturated double bond containing 0.8 to 20.0 equivalents of an ethylenically unsaturated double bond;
An epoxy compound containing 0.8 to 20.0 equivalents of an epoxy group; And
An isocyanate compound containing 0.8 to 1.2 equivalents of an isocyanate group; Composition for an optical material, characterized in that it further comprises at least one selected from among. The method according to any one of claims 1 to 8,
The composition for an optical material is a composition for an optical material, characterized in that used for producing a quantum dot film. The method of claim 4,
When the composition for an optical material is analyzed by high-speed liquid chromatography (HPLC), the peak areas of the compounds of Formula 5 and 6 and the peak areas of the compounds of Formula 7 and Formula 8 are calculated by Equation 5 below. The composition for an optical material, characterized in that the X value satisfies 1.80 to 2.30:
[Equation 5]
X = the sum of the peak areas of the compound of formula 5 and the compound of formula 6 / the sum of the peak areas of the compound of formula 7 and the compound of formula 8 A 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 is a quantum dot film, characterized in that formed of the composition for an optical material of any one of claims 1 to 8 including quantum dots. A backlight unit comprising the quantum dot film of claim 11. A liquid crystal display device comprising the backlight unit of claim 12.

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