KR102217686B1 - Quantum dot and method for preparing the same - Google Patents

Abstract

The present invention relates to a quantum dot and a method of manufacturing the same, and more particularly, a polymer including a carboxyl group and a (meth)acrylate group is ligand-bonded on the surface of the quantum dot, so that the stability and optical properties of the quantum dot will be improved. I can.

Description

Quantum dot and its manufacturing method {QUANTUM DOT AND METHOD FOR PREPARING THE SAME}

The present invention relates to a quantum dot and a method of manufacturing the same.

Quantum dots (QD) are three-dimensional semiconducting nano-sized particles and exhibit excellent optical and electrical properties. For example, even if a quantum dot is made of the same material, the color of light emitted may vary depending on the size of the particle. Due to such characteristics, quantum dots are attracting attention as nanomaterials that can be used in the fields of light emitting diodes (LEDs), bio sensors, lasers, and solar batteries. In addition, quantum dots can emit various spectra from quantum dots of the same composition through the quantum limiting effect by adjusting the size, and it is possible to secure a luminous spectrum with very excellent quantum efficiency and color purity. Compared to the fluorescent dye of, it may have very excellent photostability.

In general, quantum dots using the II-VI compound semiconductor composition composed of Group II and VI elements on the periodic table are materials capable of high luminous efficiency, light stability, and light in the visible region. Has been going on. However, since it contains Cd and Hg, it can cause serious problems in terms of environmental hazards and toxicity, and can have a harmful effect on the human body when used in the bio field. In recent years, it can replace II-VI quantum dots. A large number of studies are being conducted on the binary system of group III-VI and the ternary system of group I-III-VI.

Among them, InP quantum dots, one of group III-V quantum dots, are being studied the most extensively due to their non-toxic advantages compared to group II-VI compound semiconductors, a light-emitting area similar to CdSe quantum dots, and good luminous efficiency, and InP quantum dots are visible. It is a representative III-V group quantum dot having a wide emission range from light rays to near infrared rays. However, in general, InP quantum dots exhibit a somewhat lower luminous efficiency and a relatively wide luminous half-width value compared to CdSe-based quantum dots. For this reason, many studies have been conducted to synthesize InP quantum dots having improved luminous efficiency. In order to solve these shortcomings, by effectively removing the unbonded bonding bond of phosphorus (P) on the surface of the InP quantum dot through HF etching and UV irradiation, 30-40% due to the stable surface condition. InP quantum dots with improved luminous efficiency of were also synthesized. In addition, in addition to the method of obtaining improved luminous efficiency by stably converting the surface of InP quantum dots using hydrogen fluoride etching, studies have also obtained improved luminous efficiency through passivation of the surface by a core/shell structure like II-VI quantum dots. Is being reported.

In US Patent No. 9,260,655, a polymerizer having a plurality of carboxyl group bonds together with an alkyl skeleton as a quantum dot binding ligand is used as a ligand, and a plurality of carboxyl linkage groups are used to secure the stability of quantum dot particles. However, in order to protect the quantum dot particles by bonding of the plurality of carboxyl groups, the polymer resin must be effectively surface-treated on the surface of the quantum dot particles, but the polymer alone has difficulty in bonding to the surface of the quantum dot particles.

Accordingly, there is a need to develop a technology capable of securing the stability of quantum dot particles.

U.S. Patent No. 9,260,655

Accordingly, the inventors of the present invention have conducted various studies to solve the above problems, and as a result of modifying the surface of the quantum dot particles by bonding a polymer containing a carboxyl group and a (meth)acrylate group to the surface of the quantum dot particle, the weight of the polymer When the average molecular weight is 5,000 to 15,000, the glass transition temperature is 0°C or less, and the acid value is 30 to 90 mgKOH/g, the flexibility of the polymer is improved and the steric hindrance effect is suppressed. It was confirmed that the inner carboxyl group was effectively bonded to the surface of the quantum dot particle to improve stability and optical properties.

Accordingly, the present invention is to provide a quantum dot particle having a structure capable of improving stability and optical properties and a method of manufacturing the same.

In order to achieve the above object, the present invention is a quantum dot having a core-shell structure, wherein the quantum dot includes an acrylic resin layer formed on the surface of the shell, and the acrylic resin is the following conditions (1) to (3) Is to satisfy, provides a quantum dot:

(1) a weight average molecular weight of 5,000 to 15,000;

(2) the glass transition temperature is -30 ℃ to 0 ℃; And

(3) The acid value is 30 to 90 mgKOH/g.

The present invention also provides a method for manufacturing the quantum dot, the method for manufacturing the quantum dot, (A) aliphatic acid (aliphatic acid); And an indium element-containing compound or a mixture of the indium element-containing compound and a zinc element-containing compound in a solvent to prepare a first precursor solution for forming a core;

(B) preparing a second precursor solution for forming a core by dissolving a second precursor for forming a core represented by the following Chemical Formula 6 in a solvent;

(C) mixing and heating the first precursor solution for core formation and a non-coordination solvent, and then adding and reacting the second precursor solution for core formation to form a core of quantum dots;

(D) forming a solution by mixing an aliphatic acid and a zinc element-containing compound in a solvent;

(E) dissolving at least one of sulfur and selenium in a solvent to form a solution;

(F) The core of the quantum dots obtained in the step (C), the non-coordinating solvent, the solution obtained in the (D) step, and the solution obtained in the (E) step were sequentially mixed and heated to form a shell on the core. Preparing quantum dot particles; And

(G) by reacting the quantum dot particles with an acrylic resin, it provides a method for producing a quantum dot comprising the step of preparing a quantum dot having an acrylic resin layer formed on the shell of the quantum dot particle;

[Formula 6]

In Formula 6, n is an integer of 0 to 3, and R ₁ to R ₃ are each independently hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, iso-butyl, phenyl, It is a phenyl containing a C ₁ to C ₂₀ alkyl group.

The surface of the quantum dot particles according to the present invention is modified by bonding with a polymer and a ligand including a carboxyl group and a (meth)acrylate group to modify the surface, thereby improving stability, increasing quantum yield, and slightly reducing the half width, thereby improving optical properties. have.

In addition, due to the (meth)acrylate group contained in the polymer, the compatibility of the quantum dot particles with the matrix resin may be good, and reliability after curing may be improved.

In addition, in the present invention, if the glass transition temperature of the acrylic resin used as the polymer ligand is lowered to 0°C or less and the molecular weight is adjusted to 5,000 to 15,000, the flexibility of the polymer resin is increased and the steric hindrance effect is suppressed as much as possible. A plurality of carboxylic acids may be bonded in the resin.

By binding such a polymer ligand to the surface of the quantum dot, the surface-modified quantum dot particles have improved storage stability, increased quantum yield, and slightly reduced half width, thereby improving optical properties. In addition, when a plurality of (meth)acrylate functional groups are introduced into the polymer resin for binding to the matrix resin, compatibility with the matrix resin and reliability after curing are increased.

1 is a schematic diagram showing the structure of a quantum dot according to an embodiment of the present invention.
2A to 2F are graphs for measuring weight average molecular weights of acrylic resins prepared in Preparation Examples 1,2,3,4,6,7, respectively.
3A to 3D are graphs for measuring glass transition temperatures of acrylic resins prepared in Preparation Examples 1 to 4, respectively.
4A to 4C are photographs showing the results of evaluating quantum yields of the quantum dots prepared in Examples 1 and 3 and Comparative Example 3, respectively.

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

The term "glycidyl group" as used herein has the same meaning as an epoxy group.

Quantum dots

The present invention relates to quantum dots, and to a quantum dot with improved stability by forming an acrylic resin layer on the surface.

In the present specification, "InP-based quantum dots" means quantum dots including indium (In) and phosphorus (P). InP-based quantum dots may include, for example, indium phosphite (InP) quantum dots, as well as indium zinc phosphite (InZnP) quantum dots including indium (In), phosphorus (P) and zinc (Zn), and InP/ZnS, InP/ZnSe, InP/ZnS/ZSe, InZnP/ZnS, InZnP/ZnSe and InZnP/ZnS/ZSe quantum dots including InP quantum dots and including ZnS, ZnSe or ZnS/ZnSe shells surrounding the core It may contain particles.

1 is a schematic diagram showing the structure of a quantum dot according to an embodiment of the present invention.

Referring to FIG. 1, the quantum dot 1 according to the present invention has a structure in which a core 10, a shell 20, and an acrylic resin layer 30 are sequentially stacked, and a ligand 31 is formed on the acrylic resin layer 30. ) Is included, so that the acrylic resin layer 30 may be formed on the surface of the shell 20 through ligand bonding with the shell 20.

For example, a quantum dot according to an embodiment of the present invention may have a structure in which an acrylic resin is ligand-bonded to an InP/ZnS quantum dot including a ZnS (zinc sulfide) shell surrounding the InP quantum dot.

Hereinafter, the quantum dots of the present invention will be described in more detail into a core, a shell, and an acrylic resin layer.

[core]

In the quantum dot of the present invention, the core may include a III-V group compound.

The group III-V compound is GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, or a mixture thereof; GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs AlPSb, InNP, InNAs, InNSb, InZnP, InPAs, InPSb or mixtures thereof; And GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, GaAlNP, InAlNP, InAlNAs, InAlNSb, InAlPAs, or mixtures thereof; may include one or more selected from the group consisting of.

Alternatively, the core may be a compound containing In, Zn and P elements, and preferably, the core may contain InP and/or InZnP.

[Shell]

In the quantum dots of the present invention, the shell may include one or more selected from the group consisting of Al, Si, Ti, Mg, Zn, Se, and S.

Alternatively, the shell may include at least one selected from the group consisting of Zn, Se and S, and preferably, the shell may include ZnS, ZnSe or ZnS/ZnSe.

In addition, the shell may be formed in the form of a layer on the surface of the core, and the thickness may be 2 to 10 nm, preferably 3 to 8 nm. When the shell is formed in such a thickness range, it serves as a protective layer for the core, thereby improving the stability of the quantum dots and improving the luminous efficiency of the quantum dots.

[Acrylic resin layer]

In the quantum dots of the present invention, the acrylic resin layer is formed on the surface of the quantum dots, thereby improving the storage stability and quantum yield of the quantum dots, and reducing the half width to improve optical properties.

In the present invention, the acrylic resin (A) contained in the acrylic resin layer satisfies the following conditions (1) to (3), and may further satisfy the following conditions (4):

(1) a weight average molecular weight of 5,000 to 15,000;

(2) the glass transition temperature is -30 ℃ to 0 ℃;

(3) an acid value of 30 to 90 mgKOH/g: and

(4) (meth)acrylate equivalent is 150 to 500 g/eq.

The acrylic resin can be easily bonded to the surface of the shell by a carboxyl functional group, and can be easily bonded to the matrix resin in the quantum dot manufacturing process by the (meth)acrylate functional group, and reliability after curing can be improved.

The acrylic resin may be included in 3 to 50% by weight, preferably 4 to 40% by weight, based on the total weight of the quantum dots. If it is less than the above range, the effect of enhancing the stability of the quantum dot may be lowered, and if it exceeds the above range, the luminous efficiency of the quantum dot may be reduced.

The acrylic resin according to the present invention is characterized by having a low glass transition ion degree and a weight average molecular weight, and a high (meth)acrylate equivalent.

In addition, the weight average molecular weight of the acrylic resin may be defined as a weight average molecular weight (Mw) in terms of polystyrene, and the weight average molecular weight in terms of polystyrene is 5,000 to 15,000, preferably 7,000 to 12,000, more preferably 9,000 to 11,000 days. I can. If it is less than the above range, it is difficult to sufficiently protect the quantum dot particles, and if it is more than the above range, it is difficult to bond with the quantum dot particles, so that a problem may occur in dispersibility of the quantum dot particles.

The glass transition temperature (Tg) of the acrylic resin may be -30°C to 0°C, preferably -25°C to -5°C, and more preferably -20°C to -10°C. If it is less than the above range, adhesion may be reduced, and if it is more than the above range, coatability and developability may be reduced.

In addition, the (meth)acrylate equivalent of the acrylic resin may mean the sum of the acrylate equivalent and the methacrylic equivalent. The (meth)acrylate equivalent may be 150 to 500 g/eq, preferably 200 to 400 g/eq, more preferably 250 to 350 g/eq. If it is less than the above range, the curing density after exposure is lowered and heat resistance may be weakened, and if it exceeds the above range, coating properties and developability may be reduced.

In addition, the acid value in terms of solid content of the acrylic resin may be 30 to 90 mg·KOH/g, preferably 40 to 80 mg·KOH/g, more preferably 50 to 70 mg·KOH/g. When included in the above range, it may be advantageous in improving stability by bonding to the surface of the quantum dot.

The acrylic resin according to the present invention may include a compound represented by the following Formula 1:

[Formula 1]

,

,

,

,

,

,

,

및

중 선택되는 1종 이상을 포함하며, o, p, q는 각각 독립적으로 동일 또는 상이하며, o는 0 내지 0.2의 실수이고, p는 0.3 내지 0.9의 실수이며, q는 0.1 내지 0.5의 실수이고, o+p+q=1 이다.In Formula 1, Y is hydrogen or methyl, Q is a straight chain and pulverized C ₄ to C ₂₀ alkyl or a straight chain and pulverized C ₄ to C ₂₀ alkoxy alkyl, and Z is

,

,

,

,

,

,

,

And

Includes at least one selected from among, o, p, and q are each independently the same or different, o is a real number from 0 to 0.2, p is a real number from 0.3 to 0.9, and q is a real number from 0.1 to 0.5 , o+p+q =1.

The acrylic resin according to the present invention may include a compound represented by a formula selected from Formulas 1-1 to 1-12:

[Formula 1-1] [Formula 1-2]

[Formula 1-3] [Formula 1-4]

[Formula 1-5] [Formula 1-6]

[Formula 1-7] [Formula 1-8]

[Formula 1-9] [Formula 1-10]

[Formula 1-11] [Formula 1-12]

O, p, q, o ₁ , o _2, p _1, p ₂ of Formulas 1-1 to 1-12 are each independently the same or different, and o ₁ , o ₂ and o are each real number of 0 to 0.2 , p _1, p ₂ and p are each a real number of 0.3 to 0.9, q is a real number of 0.1 to 0.5, o=o ₁ +o ₂ , p=p ₁ +p ₂ , o+p+q =1.

In the present invention, the solid content of the acrylic resin may be 30 to 50% by weight, preferably 32 to 48% by weight, more preferably 35 to 45% by weight. If it is less than the above range, adhesion may be reduced, and if it is more than the above range, coatability and developability may be reduced.

In the present invention, the viscosity of the acrylic resin may be 30 to 100 cPs, preferably 40 to 90 cPs, more preferably 50 to 80 cPs. If it is less than the above range, adhesion may be reduced, and if it is more than the above range, coatability and developability may be reduced. In this case, the viscosity may mean the viscosity at 25° C. of the solid content of the acrylic resin, more specifically 38 wt% of the solid content and the viscosity at 25° C.

Method for producing quantum dot particles

The present invention also relates to a method of manufacturing a quantum dot, the method of manufacturing the quantum dot (A) aliphatic acid (aliphatic acid); And an indium element-containing compound or a mixture of the indium element-containing compound and a zinc element-containing compound in a solvent to prepare a first precursor solution for forming a core; (B) preparing a second precursor solution for forming a core by dissolving a second precursor for forming a core represented by the following Chemical Formula 6 in a solvent; (C) mixing and heating the first precursor solution for core formation and a non-coordination solvent, and then adding and reacting the second precursor solution for core formation to form a core of quantum dots; (D) forming a solution by mixing an aliphatic acid and a zinc element-containing compound in a solvent; (E) dissolving at least one of sulfur and selenium in a solvent to form a solution; (F) The core of the quantum dots obtained in the step (C), the non-coordinating solvent, the solution obtained in the (D) step, and the solution obtained in the (E) step were sequentially mixed and heated to form a shell on the core. Preparing quantum dot particles; And (G) reacting the quantum dot particles with an acrylic resin to prepare a quantum dot in which an acrylic resin layer is formed on the shell of the quantum dot particles; may include:

[Formula 6]

In Formula 6, n is an integer of 0 to 3, and R ₁ to R ₃ are each independently hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, iso-butyl, phenyl, It is a phenyl containing a C ₁ to C ₂₀ alkyl group.

Hereinafter, a method of manufacturing the quantum dot will be described in more detail for each step. The core-shell structured quantum dots produced below may be core-shell InP/ZnS quantum dots containing InP and ZnS in the shell, and an acrylic resin layer formed on the shell surface of the quantum dots. have.

[Step (A)]

(A) aliphatic acid; And an indium element-containing compound or a mixture of the indium element-containing compound and a zinc element-containing compound in a solvent, to prepare a first precursor solution for forming a core.

The aliphatic acid may be at least one selected from lauric acid and oleic acid.

The indium element-containing compound may be Indium Acetate.

The zinc element-containing compound may be zinc acetate.

The solvent is 1-octadecene, dodecene, tetradecane, octyl ether, phenyl ether, trioctylamine, oleyl amine, di Selected from the group consisting of ethanolamine, triethanolamine, oleyl alcohol, glycerin, diethylene glycol, tripropylene glycol methyl ether, ethyl carbitol acetate, and butyl carbitol acetate It may be one or more.

The indium element-containing compound or a mixture of the indium element-containing compound and a zinc element-containing compound; And an aliphatic acid; may have a molar ratio of 1:2 to 1:5. The molar ratio is related to the size and light absorption characteristics of the generated InP/ZnS quantum dots, and out of the above range, the light absorption characteristics of the generated InP/ZnS quantum dots may deteriorate.

In addition, by removing by-products after heating at a temperature of 80 to 180° C. after mixing, the raw materials may be uniformly mixed so as to show the physical properties of the raw material well.

[Step (B)]

In step (B), a second precursor solution for forming a core may be prepared by dissolving a second precursor for forming a core represented by the following Formula 6 in a solvent, and the solvent may be trioctyl phosphine:

[Formula 6]

In Formula 6, n is an integer of 0 to 3, and R ₁ to R ₃ are each independently hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, iso-butyl, phenyl, It is a phenyl containing a C ₁ to C ₂₀ alkyl group.

[Step (C)]

In step (C), the first precursor solution for core formation and the non-coordination solvent are mixed and heated, and then the second precursor solution for core formation is added and reacted to form a core of quantum dots. I can.

The non-coordinating solvent is a solvent in which coordination bonding is impossible, and is not particularly limited as long as it is a solvent that does not affect the reaction during the production of quantum dots. For example, the non-coordinating solvent may include at least one selected from an alkyl-based solvent, an aromatic solvent, and an ether-based solvent. Specifically, the non-coordinating solvent may be 1-octadecene, dodecene, tetradecane, octyl ether, phenyl ether, or the like.

The heating temperature may be 200° C. to 300° C., and when heated at such a heating temperature, an optimum reaction state is formed and mixed to produce a core of quantum dots having excellent luminous efficiency and uniformity. I can.

The solution after the reaction in step (C) may be cooled, and the cooling is not particularly limited as long as the temperature raised by the heating in step (C) is lowered to a room temperature level.

In addition, purity may be improved by precipitating and purifying the core of the quantum dots in the cooled solution.

[Step (D)]

In step (D), the aliphatic acid and the zinc element-containing compound may be mixed in a solvent to form a solution.

The aliphatic acid may be at least one selected from lauric acid and oleic acid.

The zinc element-containing compound may be zinc acetate.

The solvent is 1-octadecene, dodecene, tetradecane, octyl ether, phenyl ether, trioctylamine, oleyl amine, di Selected from the group consisting of ethanolamine, triethanolamine, oleyl alcohol, glycerin, diethylene glycol, tripropylene glycol methyl ether, ethyl carbitol acetate, and butyl carbitol acetate It may be one or more.

In addition, by removing by-products after heating at a temperature of 80 to 180° C. after mixing, the raw materials may be uniformly mixed so as to show the physical properties of the raw material well.

[Step (E)]

In step (E), at least one of sulfur and selenium may be dissolved in a solvent to form a solution.

The solvent may be trioctylphosphine.

[Step (F)]

In step (F), the core of the quantum dots obtained in step (C), the non-coordinating solvent, the solution obtained in step (D), and the solution obtained in step (E) are sequentially mixed and heated to form the core. It is possible to manufacture the quantum dot particles in which the shell is formed.

The non-coordinating solvent is 1-octadecene, dodecene, tetradecane, octyl ether, phenyl ether, trioctylamine, oleyl amine. , Diethanolamine, triethanolamine, oleyl alcohol, glycerin, diethylene glycol, tripropylene glycol methyl ether, ethyl carbitol acetate, and butyl carbitol acetate It may be one or more selected from.

Specifically, the core of the quantum dots obtained in step (C), the non-coordinating solvent, and the solution obtained in step (D) may be first mixed and heated. In this case, the heating temperature may be 80 to 200°C, and when heated to the heating temperature, reactivity in continuous reactions may be improved without deteriorating the physical properties of the mixed materials.

Thereafter, the solution obtained in step (E) may be further mixed and heated, at this time, the heating temperature may be 200°C to 350°C.

The manufactured quantum dot particles include InP or InZnP as a core, and InP/ZnS, InP/ZnSe, InP/ZnS/ZSe, InZnP/ZnS, InZnP/ZnSe including ZnS, ZnSe, and ZnS/ZnSe shells surrounding the core. And InZnP/ZnS/ZSe quantum dot particles.

The quantum dot particles may be cooled, precipitated, and purified to prepare a core-shell structured quantum dot particle.

[Step (G)]

In step (G), by reacting the quantum dot particles obtained in step (F) with an acrylic resin, a quantum dot having an acrylic resin layer formed on the shell of the quantum dot particles may be prepared.

The manufacturing method of the acrylic resin is as described later.

Manufacturing method of acrylic resin (A)

The present invention also relates to a method for preparing an acrylic resin (A) as described above, and may be prepared by a one-step reaction, a two-step reaction, and a three-step reaction as follows.

The first step reaction is a reaction step of preparing a vinyl or acrylic copolymer resin containing a glycidyl group, and the second step reaction is a reaction step of preparing a vinyl or acrylic copolymer resin containing a (meth)acrylate functional group. , The three-step reaction is a reaction step of preparing an acrylic resin by acid modification of a secondary alcohol.

The manufacturing method of the acrylic resin according to the present invention comprises (S1) a glycidyl group by polymerization of a first monomer (1m) containing an epoxy group and an ethylenically unsaturated group and a third monomer (3m) containing an ethylenically unsaturated group. One step reaction to form a vinyl or acrylic copolymer resin (1P);

(S2) By reacting a vinyl or acrylic copolymer resin (1P) containing a glycidyl group and a fourth monomer (4m) containing a (meth)acrylate and a carboxyl group formed in the first step reaction, a hydroxyl group and (meth) A two-step reaction of forming a vinyl or acrylic copolymer resin (2P) containing an acrylate functional group; And

(S3) The reaction of a hydroxyl group and an acid anhydride of a vinyl or acrylic copolymer resin (2P) including a hydroxyl group and a (meth)acrylate functional group formed in the two-step reaction to form an acrylic resin containing a carboxylic acid It may include a three-step reaction.

In addition, in the step (S1), the second monomer (2m), which is a (meth)acrylate, may be simultaneously polymerized.

Hereinafter, a method of manufacturing the acrylic resin (A) in each step will be described in more detail.

[Step 1 reaction]

In the method for producing an acrylic resin (A) according to the present invention, the first-step reaction is a reaction step of preparing a vinyl or acrylic copolymer resin (1P) containing a glycidyl group.

Reaction Scheme 1 below shows an example of the one-step reaction. Reaction Scheme 1 below is only an example of the first step reaction, and the first step reaction is not limited thereto.

0.3 to 0.9 moles of the first monomer (1m) containing the epoxy group and the ethylenically unsaturated group based on 1 mole of the total number of moles of the monomers used in the first step reaction; 0 to 0.2 moles of the second monomer (2m) which is a (meth)acrylate; And 0.3 to 0.9 mol of a third monomer (3m) including an ethylenically unsaturated group; may be polymerized.

<Reaction Scheme 1>

,

,

,

,

,

,

,

및

중 선택되는 1종 이상을 포함하며, o는 0 내지 0.2의 실수이고, p는 0.3 내지 0.9의 실수이며, q는 0.1 내지 0.5의 실수이고, o+p+q=1 이다.In the above Scheme 1, Y is hydrogen or methyl, Q is a straight chain and pulverized C ₄ to C ₂₀ alkyl or a straight chain and pulverized C ₄ to C ₂₀ alkoxy alkyl, and Z is

,

,

,

,

,

,

,

And

It includes at least one selected from among, o is a real number from 0 to 0.2, p is a real number from 0.3 to 0.9, q is a real number from 0.1 to 0.5, and o+p+q =1.

Referring to Scheme 1, the first-step reaction is a vinyl or acrylic copolymer resin (1P) containing a glycidyl group by copolymerizing a first monomer (1m), a second monomer (2m), and a third monomer (3m). Can be manufactured.

The first monomer (1m) may be a monomer including an epoxy group and an ethylenically unsaturated group.

The monomer containing an epoxy group and an ethylenically unsaturated group defined as the first monomer may be 0.3 to 0.9, preferably 0.4 to 0.8, when the sum of all monomers is 1 based on the content p . The amount of the monomer containing the epoxy group and the ethylenically unsaturated group, which is the first monomer, is a major factor in controlling the acid value through the amount of (meth)acrylate introduced in the second-stage reaction as described below and acid modification of the secondary alcohol in the third-stage reaction. Therefore, it is preferable to appropriately adjust the content according to the molecular weight and glass transition temperature of the vinyl or acrylic copolymer resin (1P) containing the glycidyl group.

If the p is less than the above range, there is a problem in adjusting the acid value later, and it is difficult to introduce sufficient (meth)acrylate to the vinyl or acrylic copolymer resin (1P) containing a glycidyl group, and the (meth)acrylate equivalent is increased. A problem may occur, and a problem may occur in heat resistance, and if it exceeds the above range, it may be impossible to control the glass transition temperature.

Examples of monomers containing an epoxy group and an ethylenically unsaturated group as the first monomer include glycidyl (meth)acrylate, glycidyl butyl (meth)acrylate, 2-{[(4-vinylbenzyl)oxy]methyl} One or more types of oxirane, 2-(4-vinylphenyl) oxirane, 3,4-epoxy-cyclohexyl methyl (meth)acrylate, and the like may be selected and used. Preferably, a compound represented by the following Formula 2 or Formula 3 may be used:

[Chemical Formula 2] [Chemical Formula 3]

In Formula 2 or Formula 3, Y is hydrogen or methyl.

이하인 (메타)아크릴레이트 단량체일 수 있다.When the second monomer (2m) is polymerized as a homopolymer, the glass transition temperature is -40

It may be the following (meth) acrylate monomer.

이하인 것을 특징으로 한다. 호모 폴리머로 중합시 유리전이온도는 "Polymer Handbook" 4판 John Wiley and Sons, Inc.의 VI/193~268를 참조할 수 있다. When the second monomer is polymerized with a homopolymer, the glass transition temperature is -40

It is characterized by the following. For the glass transition temperature during polymerization with a homopolymer, refer to VI/193~268 of John Wiley and Sons, Inc., 4th edition of "Polymer Handbook".

In addition, the second monomer may be defined as a (meth) acrylate monomer, and may be a (meth) acrylate compound containing mostly aliphatic alkyl. Examples include 2-ethylbutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, heptyl acrylate, hexyl acrylate, 3-methoxybutyl acrylate, 2-methoxyethyl acrylate, 3-meth Toxoxypropyl acrylate, 3-methylbutyl acrylate, lauryl acrylate, nonyl acrylate, octyl acrylate, 2-octyl acrylate, n-pentyl acrylate, propyl acrylate, decyl methacrylate, lauryl methacrylic Rate, dodecyl methacrylate, octadecyl methacrylate, octyl methacrylate may be used by selecting one or more compounds from the group.

The third monomer (3m) may be a monomer having a glass transition temperature of -40°C or higher when polymerized into a homopolymer and containing an ethylenically unsaturated group.

When polymerized with the homopolymer of the third monomer (3m), the glass transition temperature may be -40°C or higher, preferably 0°C or higher, and more preferably 50°C or higher.

In addition, the third monomer (3m) may include an ethylenically unsaturated group and a structure capable of increasing the glass transition temperature. A structure capable of increasing the glass transition temperature may be an aromatic group, a cyclic alkyl, or the like.

In addition, the third monomer (3m) is styrene, vinyltoluene, phenoxy ethyl (meth) acrylate, thiophenyl ethyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate , Dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and the like.

In the case of the third monomer, it may not be added or added according to the glass transition temperature of the acrylic binder resin 1P containing the glycidyl (epoxy) group. The content q of the third monomer is 0.1 to 0.5, preferably 0.2 to 0.4 when the total monomer content is 1.

In addition, among the third monomers (3m) containing ethylenically unsaturated groups, a third monomer (3m_SM) having a glass transition temperature of -40°C or less of the homopolymer and a material having a glass transition temperature of the homopolymer exceeding -40°C. The weight ratio (3m_HM/3m_SM) of 3 monomers (3m_HM) may be 0 to 1/5.

For the production of a vinyl or acrylic copolymer resin (1P) containing a glycidyl group in the one-step reaction, known manufacturing methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations may be appropriately selected, but preferably solution The polymerization method is good. Moreover, any of a random copolymer, a block copolymer, a graft copolymer, etc. may be sufficient as the acrylic binder resin obtained, and is generally manufactured with a random copolymer. In addition, in solution polymerization, as a polymerization solvent, ethyl acetate, toluene, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol methyl ether, isopropyl alcohol, acetone, etc. are used as a polymerization solvent. In particular, the present invention is characterized by an alkali-soluble binder structure that is designed in a structure capable of developing at a relatively low acid value.Thus, it is not necessary to use a solvent such as isopropyl alcohol or propylene glycol methyl ether among the aforementioned solvents. It is possible to solve the problem of generating a precipitate due to a compatibility problem in the step reaction. Alcohol-based solvents have a low dilution power to increase the viscosity of acrylic resins and compositions using the same, and when the viscosity of the composition is high, there is a problem that the flatness degree is lowered during coating.

Among the solvents of the acrylic resin of the present invention, even if an alcohol-based solvent is not used, there is no problem in compatibility such as occurrence of precipitates. As a specific example of solution polymerization, the reaction is carried out under a flow of an inert gas such as nitrogen, a polymerization initiator is added, and reaction conditions are usually performed at about 50 to 12°C for about 5 to 30 hours. The polymerization initiator, chain transfer agent, emulsifier, and the like used in the radical polymerization are not particularly limited and may be appropriately selected and used. In addition, the weight average molecular weight of the acrylic binder resin containing a glycidyl (epoxy) group can be controlled by the amount of the polymerization initiator and the chain transfer agent used, and the reaction conditions, and the amount thereof is appropriately adjusted according to these types. As the polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane)dihydrochloride, 2,2'-azobis[2-( 5-methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N,N' -Dimethyleneisobutylamidine), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate (trade name: VA-057, manufactured by Kowa Pure Chemical Industries, Ltd.) Azo initiators such as, potassium persulfate, persulfates such as ammonium persulfate, di(2-ethylhexyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, di-sec-butylperoxydi Carbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3 -Tetramethylbutylperoxy-2-ethylhexanoate, di(4-methylbenzoyl)peroxide, dibenzoylperoxide, t-butylperoxyisobutylate, 1,1-di(t-hexylperoxy) Peroxide-based initiators such as cyclohexane, t-butyl hydroperoxide, and hydrogen peroxide, redox initiators in which a peroxide and a reducing agent such as a combination of persulfate and sodium hydrogen sulfite, and a combination of peroxide and sodium ascorbate, and the like are mentioned. , Is not limited to these. The polymerization initiator may be used alone or in combination of two or more, and is preferably 1 to 15 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the total amount of the monomer component. It is good. Depending on the amount of the polymerization initiator, the weight average molecular weight (Mw) of the acrylic binder resin containing the glycidyl (epoxy) group can be adjusted, and as the amount of the polymerization initiator increases, the weight average molecular weight decreases. As the amount of the initiator decreases, the weight average molecular weight increases. The weight average molecular weight of the binder used in the colored photosensitive resin composition and the photosensitive resin composition for forming transparent pixels showing the effect in the present invention is 5,000 to 15,000, and to prepare the binder of the weight average molecular weight, the amount of polymerization initiator is used within the above range. It is desirable to do.

[2-step reaction]

In the method for producing an acrylic resin (A) according to the present invention, the two-step reaction is a reaction step of preparing an acrylic binder resin containing a (meth)acrylate functional group. Specifically, in the two-step reaction, an acrylic binder resin (1P) containing a glycidyl group prepared in the first step reaction, and a monomer containing a (meth)acrylate and a carboxyl group are reacted, and a (meth)acrylate functional group It is possible to prepare an acrylic binder resin containing.

Reaction Scheme 2 below shows an example of the two-step reaction. Scheme 2 below is only an example of the two-step reaction, and the two-step reaction is not limited thereto.

<Reaction Scheme 2>

In Scheme 2, Y, Q, Z, o, p, and q are the same as in Scheme 1.

Referring to Scheme 2, it is possible to obtain an acrylic binder resin (2P) containing a (meth)acrylate functional group from the acrylic binder resin (1P) containing a glycidyl group prepared in the first step reaction.

In Reaction Scheme 2, the acrylic binder resin (1P) containing a glycidyl group may be reacted with a monomer (not shown) containing a (meth)acrylate and a carboxyl group. In this case, the monomer including the (meth)acrylate and carboxyl group may be referred to as a fourth monomer (4m).

The fourth monomer (4m) may be used in 0.8 to 1.2 moles per 1 mole of the first monomer (1m) containing an epoxy group and an ethylenically unsaturated group used in the first step reaction, and in this case, the prepared (meth)acrylic The yield of the acrylic binder resin (2P) containing a rate functional group may be good.

The fourth monomer (4m), a monomer including a (meth)acrylate and a carboxyl group, may be a compound represented by the following Formula 4 or a compound represented by the following Formula 5:

[Formula 4]

In Formula 4, R ₁ is selected from the following Formulas 4-1 to 4-5, and R ₂ is a linear, branched, or cyclic carbon number of 1 to without or including an unsaturated group. 20 aliphatic or aromatic hydrocarbons with or without heteroatoms, R ₃ is hydrogen or methyl:

<Formula 4-1>

<Formula 4-2>

<Formula 4-3>

<Formula 4-4>

<Formula 4-5>

In Formulas 4-1 to 4-5, x may each independently be the same or different, and are integers of 0 to 10, and a and b are integers of 1 to 9, respectively.

[Chemical Formula 5]

In Formula 5, (meth)acrylic acid average polymerization degree n is an integer of 0 to 9, Y is hydrogen or methyl.

Scheme 3 below shows various reactions for preparing the compound represented by Chemical Formula 4.

<Reaction Scheme 3>

In Reaction Scheme 3, R ₂ of the (meth)acrylate compound containing a hydroxyl group is a linear, branched or cyclic C1-C20, hetero It is an aliphatic or aromatic hydrocarbon with or without atoms.

Referring to Scheme 3, the compound of Formula 4 may be prepared by reaction of an acid anhydride and a (meth)acrylate containing a hydroxyl group.

The reaction of the acid anhydride with the (meth)acrylate compound containing the hydroxyl group is from 0.8 mol to 1.2 mol of the acid anhydride, preferably from 0.9 mol to 1 mol of the (meth) acrylate compound containing the hydroxyl group. It is recommended to use 1.0 mole. In particular, when the acid anhydride is excessive, the acid anhydride may remain even after the reaction. The residual acid anhydride may inhibit the sensitivity of the colored photosensitive resin composition and the photosensitive resin composition for forming a transparent pixel, so it is preferable to minimize the residual acid anhydride.

In the present invention, when preparing the compound of Formula 4, the remaining acid anhydride was confirmed that the acid anhydride characteristic peaks of 1710cm ^-1 and 1920cm ^-1 were completely disappeared, and the reaction was terminated. A compound, that is, a (meth)acrylate compound containing a carboxylic acid can be prepared.

The acid anhydride can be used regardless of any acid anhydride that can be easily purchased and used by a person skilled in the art, examples of which include succinic anhydride, maleic anhydride, glutaric anhydride, suberic anhydride, phthalic anhydride, tetrahydrophthalic anhydride. , Hexahydrophthalic anhydride, trimellitic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, n-octadecyl succinic anhydride, n-octenyl succinic anhydride, n-tetradecyl One or more types of succinic anhydride and tetrapropenyl succinic anhydride may be selected and used, preferably one or more selected from the group of succinic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. Can be used.

Reaction Scheme 4 below is an example showing a reaction for preparing a (meth)acrylate compound containing the hydroxyl group.

<Reaction Scheme 4>

In Scheme 4, R ₃ is hydrogen or methyl, and n is an integer from 1 to 10.

Referring to Scheme 4, the (meth)acrylate compound (OH-MAet) containing a hydroxyl group may be derived from (meth)acrylic acid, specifically, (meth)acrylic acid (MAA), and ethylene oxide ( EO), propylene oxide (PO), or tetrahydrofuran (THF). In this case, the (meth)acrylate compound (OH-MAet) containing a hydroxyl group may include an ether group.

In addition, since the ether group generated in the (meth)acrylate compound containing a hydroxyl group prepared by the above reaction can increase the polarity, the sensitivity of the photosensitive resin composition can be improved, the structure of the repeating unit and the alkyl group is appropriately adjusted. Thus, the structure of the (meth)acrylate compound containing the hydroxyl group can be controlled.

The (meth)acrylate compound containing the hydroxyl group is 2-hydroxy ethyl (meth) acrylate, 2-hydroxy propyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) ) It may be one or more selected from the group consisting of acrylate, polypropylene glycol mono (meth) acrylate and polytetramethylene glycol mono (meth) acrylate.

Reaction Scheme 5 below is another example showing a reaction for preparing a (meth)acrylate compound containing the hydroxyl group.

<Reaction Scheme 5>

In Scheme 5, R ₂ is a linear, branched or cyclic aliphatic or aromatic hydrocarbon containing or not containing an unsaturated group having 1 to 20 carbon atoms, or not containing a hetero atom. , R ₃ is hydrogen or methyl, and n is an integer of 1 to 5.

In Reaction Scheme 5, when n moles of ε-caprolactone are used per 1 mole of the (meth)acrylate (OH-MA) containing a hydroxyl group, a repeating unit of an alkyl chain having n ester groups can be obtained.

In addition, n may be 1 to 5, preferably 1 to 3, in consideration of reaction efficiency or polarity. If it exceeds the above range, it may be difficult to provide a sufficient (meth)acrylate equivalent in the acrylic resin due to high crystallinity and low transparency and high molecular weight.

Referring to Reaction Scheme 5, a (meth)acrylate compound (OH-) containing an ester-based hydroxyl group by reaction of a (meth)acrylate compound (OH-MA) containing a hydroxyl group and ε-caprolactone (CL) MAes) can be prepared.

The (meth)acrylate compound (OH-MAes) containing the ester-based hydroxyl group can also be prepared directly through reaction, and Daicel's Placcel-FA1D (n=1), Placcel, which is commercially produced and sold -FA2D(n=2), Placcel-FA3(n=3), Placcel-FA4(n=4), Placcel-FA5(n=5), Placcel-FM1D(n=1), Placcel-FM2D(n= 2), Placcel-FM3 (n=3), Placcel-FM4 (n=4), Placcel-FM5 (n=5) Miramer M-100 (n=2) by Miwon Specialty Chemicals, SR-495 by Akema You can also purchase and use (n=2).

In addition, a catalyst may be used when preparing the compound of Formula 4 above. The catalyst may be used without limitation as long as it does not react with the acid anhydride and can accelerate the reaction between the acid anhydride and the hydroxyl group.

The catalyst may include at least one selected from the group consisting of tertiary amines, basic metals, and quaternary ammonium salts. The tertiary amine is selected from trimethylamine, triethylamine and tributylamine, and the basic metal is a basic metal such as sodium hydroxide, calcium hydroxide, and sodium carbonate, trimethylammonium chloride, trimethyl ammonium bromide, triethylammonium bromide, and triethyl It is selected from ammonium chromide, and the quaternary ammonium salt may be selected from trimethyl ammonium chloride, trimethyl ammonium bromide, triethyl ammonium bromide, and triethyl ammonium chromide.

The catalyst may be used in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the compound of Formula 4, and the amount may be appropriately adjusted according to the reaction rate.

The compound represented by Formula 5 may be obtained through a Michael addition reaction of (meth)acrylic acid, and may be a (meth)acrylic acid oligomer having 1 to 10 repeating units, see the following documents. Can be manufactured with:

USP 3,888,912;

USP 4,359,564;

Polymer Latters Edition Vol. 14, p277-281, 1976; And

Marcromolecule Vol. 7 p256~258, 1974.

Referring to this document, macrocyclic polyethers, ie crown ethers, are known to activate nucleophiles by formation of “alkaline anions”. It can be seen that high molecular weight polyesters can be prepared from (meth)acrylic acid by the use of sodium or potassium carboxylates in the presence of crown ethers:

<Reaction Scheme 6>

K ⁺ represented by a circle in Scheme 6 is a cation trapped in the crown ether. In the above reaction, (meth)acrylate acid has higher reactivity in the nucleophilic addition reaction than sodium or potassium carboxylic acid as the "alkaline anion", and n moles of (meth)acrylate acid per 1 mole of potassium carboxylic acid When added, n repeating units are formed, and generally n is 1 to 9 (meth)acrylic acid oligomers can be prepared. The sodium or potassium carboxylic acid compound in the salt form may be an alkyl carboxylic acid salt, in particular, an acetic acid salt such as sodium acetate or potassium acetate, but preferably a salt of sodium (meth)acrylate or potassium (meth)acrylate. When a compound is used in the reaction, a compound of [Chemical Formula 2] with high purity can be prepared. The cyclic polyether, i.e., the crown ether, is a form linked with 1,2-ethanidiol as a basic unit. As an example of a crown ether, for 18-crown-6, where 18 means the total number of atoms constituting the ring, and 6 means the number of oxygen atoms in the atoms constituting the ring. The inside of the ring is rich in electrons and has a strong negative charge. This is because the oxygen atom constituting the ring has an unshared electron pair. Because of this negative charge, the crown ether can easily act as a Lewis base (a substance that gives electrons) and coordination with metal ions lacking electrons. In particular, it is possible to capture metal ions by coordinating with metal ions of sodium carboxylate or potassium salt as "alkaline anion" to form a complex as shown in the following reaction formula, so that (meth)acrylic acid and (meth)acrylic acid metal salt can be easily converted into liquid. It can be a mixture and can induce a reaction smoothly.

<Reaction Scheme 7>

The crown ethers include 1,4-dioxane, 9-crown-3,12-crown-4, 15-crown-5, 18-crown-6, 21-crown 7, and dibenzo-18-crown-6. A compound can be used to capture metal ions, and it is better to select the crown ether compound according to the binding strength of the metal ions. In the case of the (meth)acrylic acid metal salt used in the present invention, 15-crown-5, 18- It is desirable to select from Crown-6 and 21-Crown 7.

As another method of preparing the (meth)acrylic acid oligomer of Formula 5, an oligomer form of (meth)acrylic acid may be prepared using an anion exchange resin containing a sulfonic acid group among microreticular (Maroreticular) ion exchange resins. . Microreticular (Maroreticular) ion exchange resin is a particle composed of a copolymer of styrene monomer and divinylbenzene, and can be manufactured into spherical particles containing pores through suspension polymerization. Spherical particles can be prepared with an anion exchange resin containing a sulfonic acid group using a general aromatic sulfonation technique. The anion exchange resin containing the sulfonic acid group can be prepared simply by using (meth)acrylic acid and the ion exchange resin without a separate solvent, and the ion exchange resin can be prepared without a separate purification process. Since it can be removed through a filter, it has the advantage of being easy to manufacture. In the present invention, AMBERLYST??, an anion exchange resin containing a sulfonic acid group from Dow Chemical Co., Ltd. 15DRY was used to prepare a (meth)acrylic acid oligomer of Formula 5. In the above manufacturing method, the n value may be experimentally determined by the reaction time, the amount of the anion exchange resin containing the sulfonic acid group, and the reaction temperature, but the range is not limited. The anion exchange resin containing a sulfonic acid group may be used in an amount of 3 to 30 parts by weight based on 100 parts by weight of (meth)acrylic acid, and preferably 5 to 20 parts by weight. If the amount of the anion exchange resin containing a sulfonic acid group is less than 3 parts by weight, the reaction rate is slow or in some cases the reaction does not proceed well, the reaction time is lengthened and the reaction temperature is increased, resulting in impurities being generated. If it is more than 30 parts by weight, the reaction rate becomes too fast, it is difficult to control the reaction, and the oligomer may be gelled.

The n value of the prepared (meth)acrylic acid oligomer of Chemical Formula 5 may be calculated as an acid value by wet titration by an end group analysis method. The acid value can be defined as the number of mg of potassium hydroxide required to neutralize the carboxylic acid contained in 1 g of the (meth)acrylic acid oligomer, and the acid value decreases as the number of n increases. The n value can be confirmed by Equation 1 below.

<Equation 1>

In the preparation of the (meth)acrylate compound containing the carboxylic acid of Formula 4 or Formula 5, a polymerization inhibitor for suppressing radical polymerization of (meth)acrylate may be used.

The polymerization inhibitor may preferably be a phenolic radical polymerization inhibitor, examples of which include hydroquinone, methoxy hydroquinone, p-benzoquinone, toluhydroquinone, mono-t-butylhydroquinone, di-t-butyl Hydroquinone or the like can be used. The polymerization inhibitor can be used by appropriately selecting the type and content according to the reaction temperature or conditions.

The polymerization inhibitor is 10 to 1500 ppm, preferably 50 to 1000 ppm, more preferably 100 to 500 ppm, based on 100 parts by weight of the total (meth)acrylate compound containing the carboxylic acid of Formula 4 or Formula 5 It is good to do. When used above the above range, there is a problem that curability is deteriorated, and when used below the above range, the product purity is lowered due to radical polymerization during the reaction and the viscosity is increased, so that application to the binder resin may be difficult.

In the two-stage reaction, when reacting the acrylic binder resin (1P) containing a glycidyl group obtained from the first-stage reaction and a monomer containing a (meth)acrylate and a carboxyl group (fourth monomer, 4m), the 4m The amount of used may be 0.8 to 1.2 moles, preferably 0.9 to 1.1 moles, per 1 mole of the monomer (first monomer, 1m) containing an epoxy group and an ethylenically unsaturated group used in the first step reaction. If it is less than the above range, a large amount of glycidyl groups remain in the acrylic resin, and the polymerization reaction with the glycidyl group proceeds when reacting with the acid anhydride in the three-step reaction described later, resulting in a rapid increase in molecular weight or the acrylic resin gelation. If the above range is exceeded, the monomer (the fourth monomer, 4m) containing the (meth)acrylate and carboxyl group remains, so that when the colored photosensitive resin composition or the photosensitive resin composition for forming a transparent pixel is applied to the color filter, it is out of the high-temperature process. It can be a cause of process pollution due to gas generation.

In addition, in the two-step reaction, in order to smoothly proceed the reaction when preparing an acrylic binder resin containing a (meth)acrylate functional group, a catalyst may be used. As the catalyst, reference may be made to the epoxy (meth)acrylate reaction catalyst of References "Chemistry & Technology of UV&EB Formulation for Coatins, Inks & Paints" Volume2, "Prepolymers and Reactive Diluents for UV and EB Curable Formulations" p.43. Examples of the catalyst include inorganic alkali salts (sodium hydroxide, potassium hydroxide, sodium carbonate), organometallic salts (lithium octanorate, tinchromide, dibutyltindiraulate), tertiary amines (N, N-dimethylaniline, triethylamine). , Quaternary ammonium (triethyl benzyl ammonium hydroxide, triethyl ammonium chloride, triethyl ammonium bromide, trimethyl ammonium chloride, trimethyl ammonium bromide), phosphine (triphenylphosphine, tri(o-tonyl) phosphine, tri (p-tonyl) phosphine and tri(o-methoxyphenyl) phosphine may be optionally used in the group, and the amount of the catalyst is 0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight, based on 100 parts by weight of the solid content of the reactant. Although it is recommended to use part, the amount can be adjusted according to the chemical structure or reaction rate of the reactant, so the amount is not limited.

In addition, in order to suppress the polymerization reaction during the two-step reaction, a polymerization inhibitor used for preparing the compound of Formula 4 or 5 may be added again.

After the two-step reaction, in addition to the (meth)acrylate functional group in the side chain of the acrylic resin, secondary hydroxyl groups generated by the ring-opening reaction of the glycidyl group may be generated equal to the number of the (meth)acrylate functional groups.

[3 step reaction]

In the method for producing an acrylic resin (A) according to the present invention, the three-step reaction is a reaction step of preparing an acrylic resin by acid modification of a secondary alcohol.

In the three-step reaction, an acrylic resin may be prepared by producing a carboxylic acid by reaction of a secondary hydroxyl group and an acid anhydride generated in the two-step reaction.

Reaction Scheme 8 below shows an example of the three-step reaction. Scheme 3 below is only an example of the three-step reaction, and the three-step reaction is not limited thereto.

<Reaction Scheme 8>

In Scheme 8, Y, Q, Z, o, p, and q are the same as in Scheme 1.

Referring to Scheme 8, the secondary alcohol contained in the acrylic binder resin (2P) containing the (meth)acrylate functional group prepared in the two-step reaction reacts with an acid anhydride (AAH) to produce a carboxylic acid, Acrylic resins can be prepared.

The acid anhydride (AAH) is succinic anhydride, maleic anhydride, glutaric anhydride, suberic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, n-dodecylyl succinic anhydride, n -Tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, n-octadecyl succinic anhydride, n-octenyl succinic anhydride, n-tetradecyl succinic anhydride, and tetrapropenyl succinic anhydride and at least one selected from the group consisting of I can.

In addition, in the reaction of the secondary alcohol and the acid anhydride, a catalyst capable of smoothly promoting the reaction may be used. The catalyst may be used in the same range as the catalyst used to prepare the compound of Formula 4 or Formula 5, and the type and amount of the catalyst may vary depending on the chemical structure of the reactant, so if the reaction can proceed smoothly , Do not limit.

In the three-step reaction, the reaction is preferably carried out at 60° C. or higher, preferably 70° C. or higher, and the reaction may proceed at a temperature lower than the boiling point of the solvent used in the at least one step reaction. The remaining acid anhydride can be confirmed that the acid anhydride characteristic peaks of 1710cm ^-1 and 1920cm ^-1 of the acid anhydride characteristic pits that can be identified on FT-IR have completely disappeared, and the reaction can be terminated.

The acid anhydride is 0.1 mol to 1.0 mol, preferably 0.5 mol to 1.0 mol, more preferably 0.7 mol based on 1 mol of the first monomer (1 m) containing an epoxy group and an ethylenically unsaturated group used in the first step reaction. To 1.0 mole may be used. The amount of the acid anhydride is not limited because the amount of the acid anhydride can be determined in consideration of the glass transition ion and the weight average molecular weight of the acrylic resin. Can remain on. However, secondary alcohol does not significantly affect the properties of the quantum dot particles.

The acid value of the acrylic resin is determined by the amount of the acid anhydride in the three-step reaction. The acid value is an acid value in terms of solid content, meaning the acid value of the solid content excluding the solvent, and is preferably 30 to 90 mgKOH/g, and when the acid value in terms of solid content is less than the above range, it is not sufficiently bound to improve the stability of the quantum dot particles. Otherwise, if it is more than the above range, process efficiency may decrease.

Hereinafter, preferred embodiments are presented to aid 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 changes and modifications fall within the scope of the appended claims.

Synthesis Example: Preparation of (meth)acrylate containing carboxylic acid

Synthesis Example 1: Synthesis of succinic acid mono-(4-acryloyloxy-butyl) ether

Equipped with a mechanical stirrer, thermometer, and reflux condenser in a 4-neck 1000 mL jacketed reactor, based on 144.2 parts by weight of 4-hydroxybutyl acrylate (1.0 mol, BASF), 95 parts by weight of succinic anhydride (0.95 mol, Yongsan Chemical Co., Ltd.) , 0.5 parts by weight of triethylamine, 0.01 parts by weight of methoxy hydroquinone (Eastman, brand name HQMME) was added and the reaction was carried out at a reaction temperature of 80° C. for 4 hours, and succinic acid mono-(4-acryloyl oxide) as shown in Scheme 9 below. Cy-butyl) ether was synthesized.

For the synthesized succinic acid mono-(4-acryloyloxy-butyl) ether, FT-IR measurement was performed, and it was confirmed that the peaks of 1710cm ^-1 and 1920cm ^-1 , which are the peaks of acid anhydride characteristics, completely disappeared, and the reaction Was terminated. At this time, the acid value was 222.1 mg·KOH/g.

<Reaction Scheme 9>

[FT-IR]

2900~ 3400cm ^-1 COOH expansion peak,

1730cm- ¹ C=O expansion peak,

1610~1640cm- ¹ C=C -C=O expansion peak,

1290cm- ¹ O= CO -Expansion peak

1025cm- ¹ - CO -C=O expansion peak

Synthesis Example 2: Preparation of acrylic acid reactant

A 4-neck 500 mL jacketed reactor was equipped with a mechanical stirrer, a thermometer, and a reflux condenser, and based on 100 parts by weight of acrylic acid (LG Chemical), 18 parts by weight of 18-crown-6 ether (Aldrich), 7.6 parts by weight of sodium acrylic acid (Aldrich Co., Sodium Acrylate), 0.8 parts by weight of methoxyhydroquinone (Eastman, brand name HQMME) was added, and the reaction was performed at 80° C. for 300 hours to complete the reaction. 18-Crown-6 ether was removed through reduced pressure distillation through 60°C of the reactor internal temperature, and 300 parts by weight of toluene were mixed to remove sodium ions present in the reaction product, and the mixture was mixed with distilled water several times in a separatory funnel. After washing, toluene was distilled under reduced pressure at 60° C. to prepare an acrylate oligomer containing carboxylic acid.

At this time, the acid value of the prepared compound was 185.5 mg·KOH/g, and the n value in [Equation 1] calculated as the acid value was 3.2.

Preparation Example 1: Preparation of acrylic resin

An acrylic resin was prepared according to the following step 1 to step 3 reaction. The monomers, solvents, and initiators used in the first step reaction, and the monomer equivalent ratio of the second step reaction and the monomer equivalent weight ratio of the third step are as described in Table 1.

(1) Step 1 reaction

In a 4-neck glass flask equipped with an electronic stirrer, thermometer, reflux cooling tube, dropping funnel, and nitrogen inlet tube, 3 parts by weight of cyclohexyl methacrylate (hereinafter referred to as CHMA, Osaka Organic Chemical), glycidyl methacrylate ( 100 parts by weight of a monomer including hereinafter GMA, Dow Chemical Co.) 70 parts by weight and 27 parts by weight of 2-ethylhexyl acrylate (hereinafter 2-EHA, Dow Chemical Co., Ltd.) was added, and t, a polymerization initiator based on 100 parts by weight of the monomer -Dissolve 5 parts by weight of butyl peroxy-2-ethyl hexanorate (hereinafter referred to as HOPO, Akema Corporation) in 250 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA, SK Energy Corporation) as a solvent, and put in a dropping funnel for dropping, The temperature was raised by 90°C while stirring in a nitrogen atmosphere. The mixture of the dropping funnel for dropping was slowly added dropwise at a rate of 2 g per minute to proceed with polymerization. After the dropwise addition was completed, the temperature was raised to 110°C, and the reaction and aging proceeded for 3 hours, and the reaction was terminated.

(2) two-step reaction

After the completion of the first step reaction, the temperature inside the reactor was lowered to 25°C, and additionally 0.1 parts by weight of methoxy hydroquinone (HQMME, Eastman), 0.2 parts by weight of triphenyl phosphine (Aldrich), acrylic acid (hereinafter AA, LG Chem. ) 35.5 parts by weight was added, and the reaction temperature was slowly raised to carry out the reaction at 90° C. for 5 hours. At this time, the acid value in terms of solid solution was 1.1 mg·KOH/g, confirming that most of the acrylic acid reacted with the epoxy functional group, and the reaction was terminated.

(3) 3-step reaction

After the completion of the second step reaction, the temperature inside the reactor was lowered to 25°C, and 13 parts by weight of succinic anhydride (hereinafter, SuAn, Yongsan Chemical Co., Ltd.) and 0.1 parts by weight of triethylamine were added, and the reaction temperature was slowly raised to 3 at 75°C. The reaction proceeded further over time. Through FT-IR, the reaction product confirmed that the acid anhydride characteristic peaks of 1710cm ^-1 and 1920cm ^-1 were completely disappeared, and the reaction was terminated to prepare an acrylic resin.

The solid content of the prepared acrylic resin is 38% by weight.

Preparation Examples 2 to 10 and Comparative Preparation Examples 1 to 4

Conducted in the same manner as in Preparation Example 1, but the monomers, solvents, and initiators used in the first-stage reaction, and the monomer equivalents ratio of the two-stage reaction and the monomer equivalents ratio of the three-stage reaction were carried out as described in Tables 1 to 3, The resin was prepared.

At this time, Comparative Preparation Examples 3 to 4 were prepared acrylic resin without a three-step reaction.

Unit: parts by weight Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Manufacturing Example 4 Manufacturing Example 5 Step 1 reaction Monomer CHMA/GMA/2-EHA
(3/70/27) CHMA/GMA/2-EHA
(3/70/27) CHMA/GMA/2-EHA
(3/70/27) CHMA/GMA/2-EHA
(3/70/27) VT/GMA/n-BA
(9/53/38) solvent PGMEA (250) PGMEA (250) PGMEA (250) PGMEA (250) PGMEA (366) Initiator HOPO (5) HOPO (8) HOPO (5) HOPO (8) HOPO (3) Step 2
reaction Monomer
Equivalent ratio
(I) AA (35.5)
One AA (35.5)
One AA (35.5)
One AA (35.5)
One Synthesis Example 1 (91)
One 3-step reaction Monomer
Equivalent ratio
(II) SuAn (13)
0.26 SuAn (13)
0.26 SuAn (23)
0.47 SuAn (23)
0.47 SuAn (30.2)
0.81 o: p: q ratio 0.03:0.75:0.22 0.03:0.75:0.22 0.03:0.75:0.22 0.03:0.75:0.22 0.10:0.50:0.40 (Meth)acrylic equivalent 202.8 202.8 202.8 202.8 270.2 Molecular weight (g/mol) 9,706 7,249 11,490 8,152 14,608

Glass transition temperature (

-17.1 -27.3 -12.6 -16.2 -10.2 Acid value (mg·KOH/g) 56.7 57.2 87.7 88.3 81.6 Viscosity (cPs) 43 33 60 35 68 CHMA: cyclohexyl metaacrylate (Osaka Yuki Co., Ltd.),
GMA: Glycidyl methacrylate (Dow Chemical)
2-EHA: 2-ethylhexyl acrylate (Dow Chemical),
PGMEA: Propylene glycol mono methyl ether acetate (SK Energy)
HOPO: t-butyl peroxy-2-ethyl hexanoate (Akema Corporation),
AA: Acrylic acid (LG Chemical) SuAn: Succinic anhydride
VT: vinyl toluene (Deltech),
n-BA: n-butyl acrylate (LG Chemical Co.),
PAn: Phthalic anhydride (Aekyung Chemical)
TCDMA: Tricyclodecyl methacrylate (Hitachi Chemical, FA-513M)
MAn: Maleic anhydride (Yongsan Chemical Co.)
PGME: Propylene glycol methyl ether (Dow Chemical)

Manufacturing Example 6 Manufacturing Example 7 Manufacturing Example 8 Manufacturing Example 9 Manufacturing Example 10 Step 1 reaction Monomer TCDMA/GMA/2-EHA
(4/64/32) GMA/2-EHA
(85/15) TCDMA/GMA/n-BA (27/30/43) TCDMA/GMA/n-BA (30/30/45) CHMA/GMA/2-EHA
(20/65/15) solvent PGMEA (278) PGMEA (257) PGMEA (227) PGMEA (317) PGMEA (271) Initiator HOPO (9) HOPO (8) HOPO (5) HOPO (4) HOPO (8) Step 2
reaction Monomer
Equivalent ratio
(I) AA (32.4)
One AA (38.8)
0.9 AA (15.2)
One Synthesis Example 2 (70.2)
1.1 MAA (39.4)
One 3-step reaction Monomer
Equivalent ratio
(II) SuAn (23.4)
0.52 PAn (10.6)
0.12 SuAn (19)
0.9 SuAn (20.7)
0.98 MAn (18.8)
0.42 o: p: q ratio 0.03:0.70:0.27 0:0.88:0.12 0.18:0.32:0.50 0.20:0.30:0.50 0.18:0.70:0.12 (Meth)acrylic equivalent 222.2 185.2 476.2 430.8 218.3 Molecular weight (g/mol) 5,980 6,336 10,715 14,491 9,476 Glass transition temperature (℃) -13.8 -15.0 -1.1 -0.5 -10.4 Acid value (mg · KOH/g) 87.6 32.5 83.7 65.6 80.7 Viscosity (cPs) 36 46 43 78 60

Comparative Preparation Example 1 Comparative Preparation Example 2 Step 1 reaction Monomer CHMA/GMA
(60/40) CHMA/GMA/2-EHA
(80/10/10) solvent PGMEA (173)
PGME (74) PGMEA (100)
PGME (87) Initiator HOPO (5) HOPO (3) Step 2
reaction Monomer
Equivalent ratio
(I) AA (20.3)
One AA (5.1)
One 3-step reaction Monomer
Equivalent ratio
(II) SuAn (25.3)
0.90 SuAn (6.9)
0.98 o: p: q ratio 0.56:0.44:0.00 0.79:0.12:0.09 (Meth)acrylic equivalent 374.5 1408.8 Molecular weight (g/mol) 9,535 15,608 Glass transition temperature (℃) 67.2 7.6 Acid value (mg·KOH/g) 95.7 40.7 Viscosity (cPs) 201 152

Tables 1 to 3 show the materials used in the acrylic resin manufacturing process of Preparation Examples 1 to 10 and Comparative Preparation Examples 1 to 2, the amount used, and the physical properties of the prepared acrylic resin. At this time, the physical properties of the acrylic resin include o,p,q ratio (o:p:q), (meth)acrylate equivalent, molecular weight, glass transition temperature, acid value, and viscosity.

In Tables 1 to 3, the monomer equivalent ratio of the two-step reaction, the monomer equivalent ratio of the three-step reaction, the o,p,q ratio (o:p:q) of the acrylic resin, (meth)acrylate equivalent, molecular weight, glass transition Temperature, acid value, and viscosity measurement methods are as follows.

(1) Monomer equivalent ratio of two-stage reaction (I)

The monomer equivalent ratio (I) of the two-step reaction refers to the number of moles of the compound containing a carboxyl group and (meta) acrylate with respect to 1 mole of the compound containing an epoxy group and an ethylenically unsaturated group used in the first step reaction.

(2) Monomer equivalent ratio of 3-step reaction (II)

The monomer equivalent ratio (II) of the three-step reaction refers to the number of moles of the acid anhydride with respect to 1 mole of the compound containing the epoxy group and ethylenically unsaturated group used in the first step reaction.

(4) o,p,q ratio (o:p:q) measurement

With respect to the acrylic resin (A), the ratio of o, p, and q (o:p:q) may be calculated as a molar ratio of a monomer containing an unsaturated double bond in a one-step reaction.

The two-stage reaction and the three-stage reaction are independent of the ratio of o, p, and q, and the two-stage reaction and the three-stage reaction have the chemical structure of the monomer containing the unsaturated double bond and the epoxy functional group at the same time It can be explained as changing. Through a two-step reaction, an acrylic binder resin containing (meth)acrylate and a hydroxyl group can be prepared, and an acrylic resin (A) can be finally prepared by modifying a hydroxyl group into a carboxylic acid through a three-step reaction. .

(5) (meth)acrylate equivalent measurement

The (meth)acrylate equivalent of the acrylic resin (A) may be determined according to the amount of the compound including the carboxyl group and the (meth) acrylate at the same time. The (meth)acrylate equivalent can be determined by Equation 2 below.

<Equation 2>

(Meth)acrylate equivalent (g/eq.)

In Equation 2, the (meth)acrylate equivalent used in the two-step reaction can be calculated by Equation 3 below.

<Equation 3>

The (meta) acrylate equivalent used in the two-step reaction (g/eq.)

(6) Molecular weight measurement

The weight average molecular weight of the acrylic resin (A) was measured under the following conditions by using a gel chromophorography (GPC) method.

Device: HLC-8120GPC (Dosoh Corporation)

Column: TSK-GELG4000HXL+ TSK-GELG2000HXL serial connection

Column temperature: 40°C

Mobile phase solvent: tetrahydrofuran (THF)

Flow rate: 1.0 ml/min

Detector: R.I detector

Measurement sample concentration: 0.6 wt% in THF

Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

In addition, the graphs for measuring the weight average molecular weight of the acrylic resins prepared in Preparation Examples 1,2,3,4,6,7 are also shown in FIGS. 2A to 2F.

(7) Glass transition temperature measurement

The glass transition temperature of the acrylic resin (A) is to prepare a sample by applying the prepared acrylic resin (A) to a glass plate in a thickness of 10 μm and then completely removing the solvent in the acrylic resin (A) for 24 hours at 40° C. I did. The prepared sample was taken around 20 mg and sealed, and nitrogen was purged at a rate of 50 ml per minute using a differential scanning calorimetry (DSC) DSC Q200 of -50°C at a temperature rising rate of 10°C per minute. The temperature of the inflection point was automatically calculated and displayed by measuring in a temperature range of 100°C.

In addition, graphs for measuring the glass transition temperature of the acrylic resins each prepared in Preparation Examples 1 to 4 are also shown in FIGS. 3A to 3D.

(8) Acid value measurement

The acid value of the acrylic resin (A) is determined according to the amount of the acid anhydride used in the three-step reaction. The acid value is an acid value in terms of solid content excluding a solvent, and can be measured by the following method by the acid base titration method using an aqueous KOH solution and calculated by Equation 3 below. Weigh the sample to 1.0 ± 0.1 g and place it in a 300 mL Erlenmeyer flask, add 50 mL of a mixed solvent of methyl alcohol and toluene, and dissolve the sample completely. (If necessary, heat to dissolve and cool.) Add 3 to 5 drops of phenolphthalene solution and titrate with 0.1N-ethanol potassium hydroxide standard solution, and the end point is when the pink color of the indicator lasts for 30 seconds.

<Equation 4>

A: Amount of 0.1N potassium hydroxide standard solution required for titration (mL)

N: Normal concentration of the standard solution used

f: concentration coefficient of 0.1N potassium hydroxide solution

S: weight of sample (g)

NV: solid content (%)

(9) Viscosity measurement

The viscosity of the acrylic resin (A) was indicated by attaching a Brookfield UL Adapter to a Brookfield DV2TLV viscometer and measuring the viscosity at 25°C in cPs.

Example 1: Preparation of InP/ZnS quantum dots with acrylic resin layer formed

(1-1) Quantum dot core( InP ) formation

In order to synthesize InP core nanoparticles, indium acetate 0.05839 g (0.2 mmol), lauric acid 0.12019 g (0.6 mmol), and 1-octadecene in a 3-neck flask (1-octadecene) 10 mL was added. The flask was stirred while simultaneously removing volatile components at 110° C. and 100 mTorr for 30 minutes, and the reaction was carried out by maintaining a temperature of 270° C. in a nitrogen atmosphere until the solution became transparent.

0.02435g (0.05mmol) tris(trimethylsilyl)phosphine and trioctylphosphine (1 ml) were mixed and stirred, and then rapidly injected into the flask in front heated to 270°C in a nitrogen atmosphere. After reacting for 1 hour, the reaction was terminated by rapidly cooling. Thereafter, when the temperature of the flask reached 100° C., 10 mL of toluene was injected and transferred to a 50 mL centrifuge tube. After adding 10 mL of ethanol, it was repeatedly purified twice using a precipitation and redistribution method, and dispersed in 13 g of toluene to prepare a dispersion of quantum dot particles of an InP core. At this time, the optical density for absorption of the first exciton ( Optical density of 1 ^st excitonic absorption) was 0.3.

(1-2) Quantum dot Shell (ZnS _x Se _1-x ) formation

로 가열하여 트리옥틸포스핀에 셀레늄이 결합된 제3 화합물을 준비하였다. 상기 제조예 1에서 제조된 InP코어의 톨루엔 분산액 2.5mL 준비하여 1-옥타데센(15ml)과 위에서 제조한 제1 화합물을 포함하는 혼합물(2.4mL)을 함께 삼구 플라스크에 넣고 교반과 동시에 110℃, 200 mTorr 하에서 30분동안 휘발성 성분을 제거하는 과정을 거쳤다. 이후 비활성 기체 분위기하에서 위에서 제조한 제2 화합물(0.3 mL) 및 제3 화합물(0.3 mL)을 넣고 270℃로 가열하였다. 1시간 반응시킨 후 냉각하여, 제4 화합물인 InP/ZnS_xSe_{1 -x} 양자점을 합성하였다.To synthesize InP/ZnS nanoparticles, zinc acetate 5.5044 g (30 mmol), oleic acid 16.944 g (60 mmol), and 1-octadecene 30 mL were added to a 3-neck flask. The flask was stirred and a mixture containing the first compound dispersed by 1-octadecene made through a process of removing volatile components at 140°C and 100 mTorr for 30 minutes at the same time as stirring was stored under an inert gas at 100°C. Into a 100 mL three-necked flask, 0.9612g (30mmol) of sulfur and 15 mL of trioctylphosphine were added and heated to 80°C while stirring under a nitrogen atmosphere to prepare a second compound in which sulfur is bound to trioctylphosphine. In a 100 mL three-necked flask, 2.3691 g (30 mmol) of selenium and 15 mL of trioctylphosphine were added and stirred under a nitrogen atmosphere.

By heating to prepare a third compound in which selenium is bound to trioctylphosphine. Prepare 2.5 mL of the toluene dispersion of the InP core prepared in Preparation Example 1, and add 1-octadecene (15 mL) and a mixture (2.4 mL) containing the first compound prepared above into a three-necked flask and stirred at 110° C., Volatile components were removed under 200 mTorr for 30 minutes. Then, the second compound (0.3 mL) and the third compound (0.3 mL) prepared above were added under an inert gas atmosphere and heated to 270°C. After reacting for 1 hour, cooling was performed to synthesize a fourth compound, InP/ZnS _x Se _{1 -x} quantum dots.

(1-3) Formation of acrylic resin layer

에서 5시간 반응을 진행하여 양자점 입자의 표면의 리간드를 교환하여 제5 화합물이 포함된 혼합물을 제조하였으며 이 때, 부피를 확인하였다. 상기 제5 화합물이 포함된 혼합물에 과량의 에탄올을 넣고 원심 분리하여 상기 양자점에 존재하는 여분의 유기물을 제거하였다. 원심 분리 후 상층액은 버리고, 원심 분리된 침전물을 건조하여 중량을 측정하고 톨루엔에 분산시켜 유기용제에 안정한 양자점을 제조하였다.As a mixture and ligand containing the fourth compound InP/ZnS _x Se _{1 -x} quantum dots prepared in (1-2), 30 mg of the acrylic resin prepared in Preparation Example 1 was added, and 90

The reaction was carried out at for 5 hours to exchange the ligand on the surface of the quantum dot particles to prepare a mixture containing the fifth compound. At this time, the volume was confirmed. Excess ethanol was added to the mixture containing the fifth compound, followed by centrifugation to remove excess organic matter present in the quantum dots. After centrifugation, the supernatant was discarded, and the centrifuged precipitate was dried, weighed, and dispersed in toluene to prepare quantum dots stable in an organic solvent.

Examples 2 to 10: Preparation of InP/ZnS quantum dots with acrylic resin layer formed

Quantum dots were prepared in the same manner as in Example 1, except that the acrylic resins each prepared in Preparation Examples 2 to 10 were used as a ligand.

Comparative Examples 1 and 2: Preparation of InP/ZnS quantum dots with acrylic resin layer formed

Quantum dots were prepared in the same manner as in Example 1, except that the acrylic resin prepared in Comparative Preparation Examples 1 and 2, respectively, was used as a ligand.

Comparative Examples 3 and 4: Preparation of InP/ZnS quantum dots with acrylic resin layer formed

Quantum dots were prepared in the same manner as in Example 1, except that oleic acid (OA, oleic acid) and dodecyl mercaptan (DDM) were used as ligands.

Experimental Example: Evaluation of physical properties of quantum dots

For the quantum dots prepared in Examples 1 to 10 and Comparative Examples 1 to 4, physical properties were measured in the following manner, and the results are shown in Tables 4 and 5.

The physical properties of the quantum dot particles prepared above were measured by the following method, and the results are shown in Table 1 below.

(1) Quantum Yield (QY)

Williams et al. “Relative fluorescence quantum yields using a computer luminescence spectrometer” 1983, Analyst 108:1067. Based on the following <Equation 5>, with reference to the literature of, the relative quantum yield of the quantum dot was calculated using a fruorecein dye (a reference value for a green emission dot at an excitation wavelength of 440 nm).

<Equation 5>

The dot in the subscript refers to a quantum dot solution dispersed in toluene, and st refers to a fluorescein dye dispersed in toluene.

QY: quantum yield, I: area of emission peak, A: absorbance at excitation wavelength,

RI: refractive index in solvent

The quantum yield was measured after dispersion of the solvent and measured after 1, 2, 5, and 10 days, and the quantum yield after 10 days is indicated in the table.

(2) Half width (FWHD)

Using OTSUKA's QE-2100, the half-value rate was confirmed using the absorption and photoluminescence spectra of the quantum dot particles dispersed in toluene.

(3) Yield per 100 mL of stock solution (g)

For 100 mL of the quantum dot particle dispersion solution after the ligand exchange reaction is completed, the quantum dot particle dispersion solution on which the ligand exchange reaction is completed is added to excess ethanol and centrifuged to remove excess organic matter present in the quantum dots, and the supernatant after centrifugation is After discarding and drying the centrifuged precipitate, the measured mass (g) was confirmed and displayed in a proportional formula.

(4) Matrix resin compatibility

Miwon Specialty Chemicals M300 (trimethylol propane triacrylate) 40 parts by weight, Osaka Yuki IBOA (isoborneol acrylate) 30 parts by weight, Brno Ph.D. PETMP 26 parts by weight (Pentaerystyroc mecaptopropionate) And 2 parts by weight of the photoinitiator IGACure 184 and 2 parts by weight of Darocure TPO, and 1 part by weight of the quantum dot particles of Examples 1 to 10 and Comparative Examples 1 to 4 based on 100 parts by weight of the mixed matrix resin The dispersion was confirmed by performing ultrasonic dispersion for 30 minutes.

The dispersibility evaluation results were expressed as follows.

◎: Completely dissolved and transparent

○: Liquid is transparent, but undissolved particles are observed

△: A large amount of undissolved particles are observed or the liquid phase is opaque.

X: A state in which particles are not dissolved and precipitated

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Exchanged ligand Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Manufacturing Example 4 Manufacturing Example 5 Manufacturing Example 6 Manufacturing Example 7 Yield per 100 mL of stock solution (g) 2.24g 2.19g 2.54g 2.41g 2.53g 2.46g 1.98g Initial quantum yield QY _I (%) 88% 87% 88% 86% 87% 84% 85% Quantum yield QY _10d after 10 days (%) 73% 77% 79% 78% 76% 79% 75% Half Width (FWHD) 41 42 42 41 43 40 45 Matrix resin compatibility ◎ ◎ ◎ ◎ ◎ ◎ ○

Example 8 Example 9 Example 10 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Exchanged ligand Manufacturing Example 8 Manufacturing Example 9 Manufacturing Example 10 Manufacturing Example 11 Manufacturing Example 12 OA DDM Yield per 100 mL of stock solution (g) 2.44g 2.19g 2.52g 1.81g 1.72g 1.16g 1.52g Initial quantum yield QY _I (%) 88% 86% 84% 81% 77% 83% 74% Quantum yield QY _10d after 10 days (%) 75% 77% 76% 54% 53% 13% 42% Half Width (FWHD) 41 42 42 41 43 44 44 Matrix resin compatibility ◎ ◎ ○ X △ △ X

Referring to Table 4, as a whole, it can be seen that Examples 1 to 10 are superior to Comparative Examples 1 to 4, and specific experimental results for representative examples are shown through the drawings.

4A to 4C are photographs showing the results of evaluating quantum yields of quantum dots prepared in Examples 1 and 3 and Comparative Example 3, respectively.

Referring to FIGS. 4A to 4C, it can be seen that the decrease in quantum yield over time is minimized in Examples 1 and 2 compared to Comparative Example 3.

In the above, although the present invention has been described by limited embodiments and drawings, the present invention is not limited thereto, and the technical idea of the present invention and the following description by those of ordinary skill in the art to which the present invention pertains. It goes without saying that various modifications and variations are possible within the equivalent range of the claims to be made.

Claims (5)

In the quantum dot having a core-shell structure,
The core includes a group III-V compound, and the shell includes at least one selected from the group consisting of Al, Si, Ti, Mg, Zn, Se and S,
The quantum dot includes an acrylic resin layer formed on the surface of the shell,
The acrylic resin satisfies the conditions of the following (1) to (3),
The acrylic resin is a quantum dot containing a compound represented by the following formula (1):
(1) a weight average molecular weight of 5,000 to 15,000;
(2) the glass transition temperature is -30 ℃ to 0 ℃; And
(3) the acid value is 30 to 90 mgKOH/g,
[Formula 1]

In Formula 1, Y is hydrogen or methyl, Q is a straight chain and pulverized C ₄ to C ₂₀ alkyl or a straight chain and pulverized C ₄ to C ₂₀ alkoxy alkyl, and Z is

,

,

,

,

,

,

,

And

Includes at least one selected from among, o, p, and q are each independently the same or different, o is a real number from 0 to 0.2, p is a real number from 0.3 to 0.9, and q is a real number from 0.1 to 0.5 , o+p+q =1. The method of claim 1,
The acrylic resin is to further satisfy the conditions of the following (4), quantum dots:
(4) (meth)acrylate equivalent is 150 to 500 g/eq. The method of claim 1,
The acrylic resin is a random copolymer represented by a formula selected from Formulas 1-1 to 1-12, quantum dots:
[Formula 1-1] [Formula 1-2]

[Formula 1-3] [Formula 1-4]

[Formula 1-5] [Formula 1-6]

[Formula 1-7] [Formula 1-8]

[Formula 1-9] [Formula 1-10]

[Formula 1-11] [Formula 1-12]

O, p, q, o ₁ , o _2, p _1, p ₂ of Formulas 1-1 to 1-12 are each independently the same or different, and o ₁ , o ₂ and o are each real number of 0 to 0.2 , p _1, p ₂ and p are each a real number of 0.3 to 0.9, q is a real number of 0.1 to 0.5, o=o ₁ +o ₂ , p=p ₁ +p ₂ , o+p+q =1. The method of claim 1,
Group III-V compounds contained in the core may include GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, or a mixture thereof; GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs AlPSb, InNP, InZnP, InNAs, InNSb, InPAs, InPSb, or mixtures thereof; And GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, GaAlNP, InAlNP, InAlNAs, InAlNSb, InAlPAs, or mixtures thereof; that includes at least one selected from the group consisting of, quantum dots. The method of claim 1,
The core includes at least one selected from InP and InZnP,
The shell comprises at least one selected from ZnS, ZnSe and ZnS/ZnSe, quantum dots.

Images