KR101690871B1 - Three dimensional printing composite material and method of fabricating the same - Google Patents

Three dimensional printing composite material and method of fabricating the same Download PDF

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Publication number
KR101690871B1
KR101690871B1 KR1020150061260A KR20150061260A KR101690871B1 KR 101690871 B1 KR101690871 B1 KR 101690871B1 KR 1020150061260 A KR1020150061260 A KR 1020150061260A KR 20150061260 A KR20150061260 A KR 20150061260A KR 101690871 B1 KR101690871 B1 KR 101690871B1
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South Korea
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functional
functional particles
particles
photocurable resin
phosphor
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KR1020150061260A
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Korean (ko)
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KR20150125899A (en
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김효준
안진호
고기영
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한양대학교 산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/52—Luminescence
    • C08G2261/522—Luminescence fluorescent

Abstract

A method of making a three-dimensional printing composite material is provided. The method for producing a three-dimensional printing composite material according to the present invention includes the steps of preparing functional particles, binding a functionalized molecule having a functional group to the functional particles to convert the surface characteristics of the functional particles And dispersing the functional grains into which the surface characteristics have been converted into the photocurable resin.

Description

TECHNICAL FIELD [0001] The present invention relates to a three-dimensional printing composite material,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a three-dimensional printing composite material and a manufacturing method thereof, and more particularly, to a three-dimensional printing composite material including functional particles combined with functional molecules and a manufacturing method thereof.

Three-dimensional printing is a technique for fabricating three-dimensional shaped objects by stacking specific materials in powder, liquid, and solid form. That is, a technique of digitizing an object to be sphere with a virtual object through a three-dimensional graphic design, and then stacking very thin cross-sections one by one to produce the resultant product is called AM (Addictive Manufacturing) (Subtractive Manufacturing).

3D printing was first developed in '84, but it was used only for product models and prototypes until the 2000s. However, recent technological advances have gradually expanded the range of applications, which have led to the development of consumer products, electronic parts, automobiles, medical equipment, , Space, aviation, and other industries.

In general, materials used in three-dimensional printing include organic materials containing harmful chemicals. This may adversely affect the user, and environmental pollution such as water pollution may occur due to by-products generated in the printing process.

Accordingly, there is a need for research and development of a three-dimensional printing material that is harmless to the human body, is environmentally friendly, and has characteristics suitable for three-dimensional printing.

SUMMARY OF THE INVENTION The present invention provides a three-dimensional printing composite material having a simplified manufacturing process, and a manufacturing method thereof.

Another object of the present invention is to provide a three-dimensional printing composite material having a reduced manufacturing cost and a manufacturing method thereof.

Another object of the present invention is to provide a three-dimensional printing composite material which can be easily applied to a three-dimensional printer, and a manufacturing method thereof.

Another aspect of the present invention is to provide a three-dimensional printing composite material which is aesthetically pleasing, and a method of manufacturing the same.

Another object of the present invention is to provide a light emitting structure fabricated using a three-dimensional printing composite material.

In order to solve the above technical problems, the present invention provides a method for producing a three-dimensional printing composite material.

According to an embodiment of the present invention, there is provided a method of manufacturing a three-dimensional printing composite material, comprising the steps of preparing functional particles, binding a functionalized molecule having a functional group to the functional particles, Converting the surface characteristics, and dispersing the functional particles with converted surface characteristics in the photocurable resin.

According to one embodiment, the degree of dispersion of the functional particles in the photocurable resin can be increased by the functional groups of the functional molecules combined with the functional particles.

According to one embodiment, the step of binding the functional molecule to the functional particle may include the steps of preparing a functionalized solution having the functional particle and the functional molecule in the reactor, and evaporating the functional solution, And combining the functional molecule with the functional particle.

According to one embodiment, the step of preparing the functional particles in the reactor may include preparing a first phosphor emitting light in a first wavelength band and a second phosphor emitting light in a second wavelength band in the reactor Wherein the step of bonding the functional molecule and the functional particle may include bonding the first fluorescent material and the second fluorescent material to the functional molecule.

According to one embodiment, when the photocurable resin is hydrophobic and the functional particle is hydrophilic, the functional particle is converted into hydrophobic by the functional molecule, the photocurable resin is hydrophilic, the functional particle is hydrophobic , The functional particles can be converted into hydrophilic by the functional molecule.

In order to solve the above technical problems, the present invention provides a three-dimensional printing composite material.

According to one embodiment, the three-dimensional printing composite material may include a photo-curable resin and functional particles dispersed in the photo-curable resin and combined with a functional molecule having a functional group to convert surface characteristics.

According to one embodiment, the surface characteristics of the photocurable resin and the functional particles may be hydrophilic or hydrophobic and the same.

According to one embodiment, the functional particles include a first phosphor that emits light in a first wavelength band in response to incident light, and a second phosphor that emits light in a second wavelength band And a second phosphor that emits light.

According to one embodiment, the three-dimensional printing composite material comprises a photo-curable resin, first functional particles dispersed in the photo-curable resin and combined with a functional molecule having a functional group, the first functional particle being converted in surface characteristics, And second functional particles dispersed in the photocurable resin at a lower dispersion than the particles.

According to one embodiment, the first functional particles and the second functional particles each include a first phosphor and a second fluorescent material, and the first fluorescent material and the second fluorescent material react with each other in the same wavelength band , And can emit light of different wavelength bands.

In order to solve the above technical problem, the present invention provides a structure.

According to one embodiment, the structure may be fabricated in a three-dimensional printing process using a three-dimensional printing composite material according to the embodiments described above.

According to the embodiment of the present invention, functional particles having functional groups and functional particles are combined to convert the surface characteristics of the functional particles, and the functional particles having surface characteristics converted can be dispersed in the photocurable resin. As a result, the three-dimensional printing composite material can be dispersed substantially uniformly in the photocurable resin and thus the manufacturing process is simplified, the manufacturing cost is reduced, and the color is excellent. A manufacturing method can be provided.

1 is a flowchart illustrating a method of manufacturing a three-dimensional printing composite material according to an embodiment of the present invention.
FIGS. 2 and 3 are views for explaining a method for producing a three-dimensional printing composite material according to an embodiment of the present invention.
FIGS. 4 and 5 are views for explaining a three-dimensional printing composite material according to a first modification of the embodiment of the present invention and a method of manufacturing the same.
FIG. 6 is a view for explaining a three-dimensional printing composite material according to a second modification of the embodiment and a method of manufacturing the same.
7 is a photograph for explaining dispersion of a three-dimensional printing composite material according to an embodiment of the present invention.
8A and 8B are photographs illustrating light emission characteristics of a structure manufactured using a three-dimensional printing composite material according to an embodiment of the present invention.
9 is a photograph of a blue light emitting structure manufactured using a three-dimensional printing composite material according to an embodiment of the present invention.
10 is a photograph of a structure for emitting green light using a three-dimensional printing composite material according to an embodiment of the present invention.
11 is a photograph of a structure emitting blue and green light using a three-dimensional printing composite material according to an embodiment of the present invention.
12 is a photograph of a structure for emitting blue and green light mixed using a three-dimensional printing composite material according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the technical spirit of the present invention is not limited to the embodiments described herein but may be embodied in other forms. Rather, the embodiments disclosed herein are provided so that the disclosure can be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

Also, while the terms first, second, third, etc. in the various embodiments of the present disclosure are used to describe various components, these components should not be limited by these terms. These terms have only been used to distinguish one component from another. Thus, what is referred to as a first component in any one embodiment may be referred to as a second component in another embodiment. Each embodiment described and exemplified herein also includes its complementary embodiment. Also, in this specification, 'and / or' are used to include at least one of the front and rear components.

The singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. It is also to be understood that the terms such as " comprises "or" having "are intended to specify the presence of stated features, integers, Should not be understood to exclude the presence or addition of one or more other elements, elements, or combinations thereof.

In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In the specification of the present application, the surface property means the hydrophobic or hydrophilic property of the surface of the object.

FIG. 1 is a flow chart for explaining a method of manufacturing a three-dimensional printing composite material according to an embodiment of the present invention, and FIGS. 2 and 3 are views for explaining a method of manufacturing a three-dimensional printing composite material according to an embodiment of the present invention These are the drawings.

Referring to FIGS. 1 and 2, the functional particles 112 are prepared (S110). The functional particles 112 may be prepared in the first vessel 110 disposed in the reactor 10. The functional particles 112 may be in a powder state. According to one embodiment, the functional particles 112 may be a phosphor that emits light of various colors such as red, green, blue, cyan, magenta, and yellow in response to the emitted light. For example, the functional particles 112 may include at least one of ZnS: CuAl, SrGa2S4: Eu, ZnS: AgAl, Y2O2S: Eu, YAG: Ce or a quantum dot. Alternatively, according to another embodiment, the functional particles 112 may be various types of ceramic particles that improve the strength, hardness, and the like of a structure to be manufactured during a three-dimensional fritting process.

According to one embodiment, the functional particles 112 may be hydrophilic. Alternatively, according to another embodiment, the functional particles 112 may be hydrophobic.

In the second container 210 disposed in the reactor 10, a functional solution 212 containing a functionalized molecule may be prepared. The functional molecule may comprise a hydrophilic or hydrophobic functional group. According to one embodiment, the functional molecule may include a functional group having properties different from those of the surface of the functional particles 112. For example, when the functional particles 112 are hydrophilic, they may include a hydrophobic functional group of the functional solution 212. When the functional particles 112 are hydrophobic, the functional solution 212 may have a hydrophilic function Group.

The functional molecule may have a head group capable of easily bonding with the functional particles 112. For example, the functional molecules, ROH, RCOO-, RCCOH, RCOO-OOCR, Ene-diol, RNH 2, RC≡N, RN≡N + (BF4 -), RSH, RCSSH, RSeH, R 3 P, etc. As a head group.

The functional particles having the functional group may be bonded to the functional particles 112 to convert the surface characteristics of the functional particles 112 (S120). When the functional particles 112 are hydrophilic, the surface characteristics of the functional particles 112 can be converted to hydrophobic by the functional groups of the functional molecules bonded to the functional particles 112. Alternatively, when the functional particles 112 are hydrophobic, the surface characteristics of the functional particles 112 may be converted to hydrophilic by the functional groups of the functional molecules combined with the functional particles 112.

The step of coupling the functional molecules to the functional particles 112 comprises the steps of vaporizing the functional solution 212 in the reactor 10 to produce a vapor 214, (112). ≪ / RTI >

The inside of the reactor 10 can be converted into a vacuum condition by the vacuum pump 20 of the reactor 10 before the functional solution 212 is evaporated. Accordingly, the functional solution 212 is easily evaporated, and the vapor 214 can be easily provided to the functional particles 112.

Referring to FIGS. 1 and 3, the surface-converted functional particles 114 may be dispersed in the photocurable resin 312 in the third container 312 (S130). The photocurable resin 312 may include at least one of a (meth) acrylic acid ester monomer, an oligomer of a (meth) acrylic acid ester monomer, or a partial (meth) acrylated epoxy resin. Examples of the oligomers of the (meth) acrylic acid ester monomer and the (meth) acrylic acid ester monomer include 2-hydroxyethyl (meth) acrylate, di- or tetraethylene glycol di (meth) acrylate, (Meth) acrylate, and urethane-modified di (meth) acrylate. The partial (meth) acrylated epoxy resin can be formed by reacting a bisphenol A type epoxy resin with (meth) acrylic acid. (Meth) acrylic acid in an amount of 10 to 90 equivalent% based on 1 equivalent of an epoxy group in the presence of a basic catalyst (for example, a trivalent organic phosphoric acid compound and / or an amine compound), for example, a bisphenol A type epoxy resin and (meth) , And removing the basic catalyst by treatment such as filtration, centrifugation and / or water washing of the reaction product.

A photopolymerization initiator may be added to the third container 310. The photopolymerization initiator may be, for example, a self-cleavable benzoin compound, acetophenone, hydroxyacetophenone,? -Aminoacetophenone,? -Acyloxime ester, acylphosphine oxide compound, , Hydrogen-releasing benzophenones, benzoin ethers, benzyl ketaldehyde, dibenzosuberones, anthraquinones, xanthones, thioxanthones, halogenoacetophenones, dialkoxyacetophenones, hydroxy Acetophenone, acetophenone, acetophenone, acetophenone, acetophenone, acetophenone, acetophenone, acetophenone, halogenophenone, acetophenone, halogenobisimidazoles, or halogenogenialdehyde.

The functional particles 114 having the surface characteristics converted may have the same surface characteristics as the photocurable resin 312. For example, when the photocurable resin 312 has a hydrophobic property and the functional particle 112 has a hydrophilic property, the functional particle 112 may include the functional molecule contained in the functional solution 212, The surface characteristics are converted into hydrophobic properties, and the functional particles 114 having the hydrophobic property can be dispersed in the photocurable resin 312. The functional particles 112 may have a hydrophobic property and the functional particles 112 may have hydrophobic characteristics when the photocurable resin 312 has a hydrophilic property and the functional particles 112 have hydrophobic properties. The surface characteristics are converted into hydrophilic properties by binding with the functional molecules, and the functional particles 114 having the hydrophilic properties can be dispersed in the photocurable resin 312. Accordingly, the functional particles 114 having the surface characteristics converted into the photocurable resin 312 can be substantially uniformly dispersed.

If the functional particles and the photocurable resin have different surface characteristics (for example, the functional particles are hydrophilic and the photocurable resin is hydrophobic, or the functional particles are hydrophobic and the photocurable resin is hydrophobic, The curable resin is hydrophilic), and the functional particles may not be uniformly dispersed in the photocurable resin. When a structure is produced by a three-dimensional printing process using a three-dimensional printing material in which functional particles are not uniformly dispersed in a photocurable resin, functional particles are concentrated at a specific position of the structure, The aesthetics, merchantability, or practicality of the structure may be deteriorated.

However, as described above, according to the embodiment of the present invention, the functional particles 112 and the functional solution 212 are introduced into the reactor 10, and the functional solution 212 is evaporated, The surface properties of the photocurable resin 112 can be controlled to be the same as the surface characteristics of the photocurable resin 312 in a simplified process. As a result, the functional particles 114 can be dispersed substantially uniformly in the photocurable resin 312, thereby simplifying the manufacturing process, reducing the manufacturing cost, and providing a highly reliable A three-dimensional printing composite material and a manufacturing method thereof can be provided.

Unlike the embodiments of the present invention described above, according to the first modification of the embodiment of the present invention, the functional particles having different functions can be dispersed in the photocurable resin. Hereinafter, with reference to Figs. 4 and 5, a three-dimensional printing composite material according to a first modification of the embodiment of the present invention and a manufacturing method thereof will be described.

FIGS. 4 and 5 are views for explaining a three-dimensional printing composite material according to a first modification of the embodiment of the present invention and a method of manufacturing the same.

4, in the reactor 10, in addition to the first functional particles 112 and the functional solution 210 described with reference to FIGS. 1 and 2, Particles 122 are provided. The second functional particles 122 may have the same surface properties (hydrophobic or hydrophilic) as the first functional particles 112.

The first functional particles 112 and the second functional particles 122 may have different functions. For example, the first functional particles 112 may be ceramic particles that increase the strength, and the second functional particles 122 may be phosphors.

Alternatively, for example, the first functional particles 112 and the second functional particles 122 react with light in the same wavelength band, and the first fluorescent material and the second fluorescent material, which emit light in different wavelength bands, Respectively. In other words, when the first functional particles 112 include the first phosphor that emits light of a first wavelength in response to light to be irradiated, the second functional particles 122 react with the light to be irradiated And the second phosphor that emits light of a second wavelength. The first functional particles 114 may include Y 2 O 2 S: Eu that emits red light in response to ultraviolet rays in the wavelength band of 365 nm, and the second functional particles 122 may include 365 nm And ZnS: AgAl which emits blue light in response to ultraviolet rays of a wavelength band.

The vapor 214 in which the functional solution 212 has been evaporated may be provided to the first functional particles 112 and the second functional particles 122 as described with reference to Figures 1 and 2 . The functional molecules are combined with the first functional particles 112 and the second functional particles 122 so that the surface characteristics of the first functional particles 112 and the second functional particles 122 are different from each other, Hydrophobic to hydrophilic, or hydrophilic to hydrophobic.

5, the first functional particles 114 and the second functional particles 124 having the surface characteristics converted are dispersed in the photocurable resin 312 described with reference to FIGS. 1 and 2, Dimensional printing composite material can be manufactured. The first functional particles 114 and the second functional particles 124 having the surface characteristics converted may have the same surface characteristics as those of the photocurable resin 312. Accordingly, the first functional grains 114 and the second functional grains 124 having the converted surface characteristics can be dispersed substantially uniformly in the photocurable resin 312.

As described above, according to the first modification of the embodiment of the present invention, the first functional particles 114 and the second functional particles 124 can be uniformly dispersed in the photocurable resin 312 . Accordingly, a highly reliable three-dimensional printing composite material having various functions (for example, a function of emitting light of various colors) and a manufacturing method thereof can be provided.

According to the second modification of the embodiment of the present invention, unlike the embodiment and the first modification described above, the first functional particles having a relatively high degree of dispersion in the photo-curable resin and the first functional particles having a relatively low degree of dispersion 2 functional particles can be dispersed. Hereinafter, with reference to FIG. 6, a three-dimensional printing composite material according to a second modification of the embodiment of the present invention and a manufacturing method thereof will be described.

FIG. 6 is a view for explaining a three-dimensional printing composite material according to a second modification of the embodiment and a method of manufacturing the same.

Referring to Fig. 6, the first functional particles 114 whose surface characteristics are converted by the method described with reference to Figs. 1 and 2, and the photocurable resin 312 are prepared. The first functional particles 114 and the photocurable resin 312 having the surface characteristics converted may have the same surface characteristics as each other in terms of hydrophilicity or hydrophobicity.

The second functional particles 122 having different surface properties from the photocurable resin 312 and the first functional particles 114 are prepared. For example, when the photocurable resin 312 and the first functional particles 114 are hydrophobic, the second functional particles 122 may be hydrophilic. Alternatively, when the photocurable resin 312 and the first functional particles 114 are hydrophilic, the first functional particles 114 may be hydrophobic.

As described with reference to FIG. 5, the first functional particles 114 and the second functional particles 122 may perform different functions. For example, the first functional particles 112 may include a first fluorescent material and a second fluorescent material, which react with light of the same wavelength band and emit light of different wavelength bands, Respectively. The first functional particles 114 may include Y 2 O 2 S: Eu that emits red light in response to ultraviolet rays in the wavelength band of 365 nm, and the second functional particles 122 may include a light- And ZnS: CuAl which emits green light in response to ultraviolet rays of the band.

According to one embodiment, the second functional particles 122 are not bonded to the functional molecules of the functional solution 212 described with reference to Figs. 1 and 4, and the photocurable resin 312 and the Lt; RTI ID = 0.0 > 114 < / RTI > In other words, when the second functional particles 122 have different surface characteristics from the photocurable resin 312 and the first functional particles 114, the functional solution 212 described with reference to FIGS. 1 and 4 The surface treatment of the second functional particles 122 may be omitted. According to another embodiment, the functional particles 122 may have other surface characteristics than the photocurable resin 312 and the first functional particles 114 in combination with the functional molecules of the functional solution. In other words, when the second functional particle 122 has the same surface characteristics as the photocurable resin 312 and the first functional particle 114, the method described with reference to Figs. 1 and 4, The second functional particles 122 may be surface-treated using a solution so that the second functional particles 122 may have different surface properties from the photocurable resin 312 and the first functional particles 114 .

The first functional particles 114 having the same surface characteristics as those of the photo-curable resin 312 and the second functional particles 122 having surface characteristics different from those of the photo- (312) so that a three-dimensional printing composite material can be produced. The first functional particles 114 may be dispersed substantially uniformly in the photocurable resin 312 with a relatively high degree of dispersion and the second functional particles 122 may be dispersed in the photocurable resin 312 It can be dispersed to a relatively low dispersion. Accordingly, when a three-dimensional printing process is performed using the three-dimensional printing composite material, the first functional particles 114 can be uniformly distributed in the structure, and the second functional particles 122 can be uniformly distributed in the structure Or may be less distributed in a portion of the structure. Thus, as described above, the first functional particles 114 and the second functional particles 122 include the first phosphor and the second phosphor that emit light of different colors, as described above There can be provided a three-dimensional printing composite material capable of producing a structure having a unique color and a manufacturing method thereof.

Hereinafter, characteristics evaluation results of the three-dimensional printing composite material according to the above-described embodiment of the present invention will be described.

7 is a photograph for explaining dispersion of a three-dimensional printing composite material according to an embodiment of the present invention.

7, a Y 2 O 2 S: Eu phosphor having hydrophilic properties was prepared as functional particles by emitting red light in response to ultraviolet rays having a wavelength of 365 nm, and ARARIO 410 of Carima having hydrophobic properties was coated on a photocurable resin Lt; / RTI > Trichloro (1H 1H 2H 2H-perfluorooctyl) silane was prepared as a functional solution having a functional molecule having a hydrophobic functional group in order to convert the surface characteristics of the Y 2 O 2 S: Eu phosphor.

In accordance with an embodiment of the present invention, Y 2 O 2 S: Eu phosphor to have the same surface characteristics as the photocurable resin, Y 2 O 2 S: Eu phosphor and, and places the above-mentioned functional solution in the reactor and evaporation of the above-mentioned functional solution , And a functional molecule having a hydrophobic functional group was bonded to the Y 2 O 2 S: Eu phosphor. A Y 2 O 2 S: Eu phosphor having hydrophobic properties was dispersed in the photocurable resin to prepare a three-dimensional printing composite material and then photographed.

According to a comparative example of the embodiment of the present invention described above, a Y 2 O 2 S: Eu phosphor having hydrophilic characteristics, which is not surface-treated with the functional solution, is dispersed in the photocurable resin to form a three-dimensional printing composite material After taking a picture.

7 (a) is a photograph of a photo-curing resin in which a Y 2 O 2 S: Eu phosphor is not dispersed, and FIG. 7 (b) is a photograph showing a Y 2 O 2 S : will have taken the photo-curable resin is Eu phosphor dispersed, (c) of Figure 7 is Y 2 O 2 S having a hydrophilic property according to a comparative example of an embodiment of the present invention: the light-curing resin in which Eu phosphor is dispersed .

7, according to the embodiment of the present invention, the Y 2 O 2 S: Eu phosphor having the same surface characteristics (hydrophobic property) as the photocurable resin is substantially uniformly distributed in the photocurable resin, According to the comparative example, it is confirmed that the Y 2 O 2 S: Eu phosphor having a surface property (hydrophilic property) different from that of the above-mentioned photocurable resin was not dispersed in the photocurable resin but precipitated downward. In other words, it is confirmed that it is an efficient method of improving the dispersion degree of the functional particles in the photocurable resin by evaporating the functional solution to convert the functional particles to have the same surface characteristics as the photocurable resin.

8A and 8B are photographs illustrating light emission characteristics of a structure manufactured using a three-dimensional printing composite material according to an embodiment of the present invention.

Referring to FIGS. 8A and 8B, in accordance with an embodiment of the present invention described with reference to FIG. 7, a three-dimensional printing composite material comprising a photocurable resin in which a Y 2 O 2 S: Eu phosphor having a hydrophobic property is dispersed , And a photocurable resin in which the addition of the Y 2 O 2 S: Eu phosphor was omitted, were used to produce structures by a three-dimensional printing process. FIG. 8A is a photograph of the structures taken in the state that no light is irradiated, and FIG. 8B is a photograph taken in a state in which the structures are irradiated with ultraviolet rays of 365 nm wavelength band. Specifically, FIGS. 8A and 8B are photographs of a structure manufactured using a three-dimensional printing material including a photo-curing resin in which the dispersion of the Y 2 O 2 S: Eu phosphor is omitted 8 (b) and 8 (b) are photographs of a structure manufactured using a three-dimensional printing material including a photocurable resin in which a Y 2 O 2 S: Eu phosphor is dispersed.

8A and 8B, when the ultraviolet ray of 365 nm wavelength is irradiated, a structure manufactured using a three-dimensional printing material containing a photocurable resin in which a Y 2 O 2 S: Eu phosphor is dispersed, And the Y 2 O 2 S: Eu phosphor is substantially uniformly distributed in the structure, so that the red light emitted from the structures is uniform. In other words, it can be confirmed that it is an efficient method to produce a structure having excellent color feeling by performing a three-dimensional printing process using the three-dimensional printing composite material having improved dispersion of the functional particles in the photocurable resin .

FIG. 9 illustrates a blue light emitting structure fabricated using a three-dimensional printing composite material according to an embodiment of the present invention.

Referring to FIG. 9, a three-dimensional printing composite material was prepared by dispersing a ZnS: AgAl phosphor that emits blue light to a photocurable resin. 9 (a) to 9 (d) are graphs showing the relationship between the amounts of ZnS: AgAl fluorescent material for the photocurable resin and the three-dimensional printing composite material of 1: 0.05, 1: 0.1, 1: 0.3, Structures. It can be confirmed that blue light is emitted when ultraviolet rays of 365 nm wavelength band are irradiated to the structures including the ZnS: AgAl phosphor.

10 is a photograph of a structure for emitting green light using a three-dimensional printing composite material according to an embodiment of the present invention.

Referring to FIG. 10, a three-dimensional printing composite material was prepared by dispersing a ZnS: CuAl fluorescent material that emits green light into a photocurable resin. 10 (a) to 10 (d) are graphs showing the results of the measurement of a three-dimensional printing composite material in which the weight ratio of the ZnS: CuAl phosphor to the photocurable resin is 1: 0.05, 1: 0.1, 1: 0.3, Structures. It can be confirmed that green light is emitted when ultraviolet rays of 365 nm wavelength band are irradiated to the structures including the ZnS: CuAl phosphor.

11 is a photograph of a structure emitting blue and green light using a three-dimensional printing composite material according to an embodiment of the present invention.

11, a ZnS: AgAl fluorescent material for emitting blue light and a ZnS: CuAl fluorescent material for emitting green light are dispersed in a photocurable resin, respectively, to produce three-dimensional printing composite materials. ZnS: AgAl A three-dimensional printing composite material including a phosphor was printed, and a three-dimensional printing composite material containing ZnS: CuAl fluorescent material was printed on the right side of the substrate to prepare a structure. Fig. 11 (a) shows ultraviolet rays of 365 nm before the structure is irradiated, and Fig. 11 (b) shows ultraviolet rays of 365 nm irradiated onto the structure. As can be seen from FIG. 11, it can be confirmed that blue light and green light are simultaneously emitted from the structure corresponding to the ultraviolet light to be irradiated.

12 is a photograph of a structure for emitting blue and green light mixed using a three-dimensional printing composite material according to an embodiment of the present invention.

12, a ZnS: AgAl fluorescent material for emitting blue light and a ZnS: CuAl fluorescent material for emitting green light are dispersed in a photocurable resin to produce three-dimensional printing composite materials, and a ZnS: CuAl fluorescent material And printing a 3D printing composite material including a ZnS: AgAl fluorescent material to fabricate a structure. As can be seen from FIG. 12, blue light and green light are simultaneously emitted from the structure corresponding to ultraviolet rays of 365 nm, and a mixed light of blue light and green light is displayed.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the scope of the present invention is not limited to the disclosed exemplary embodiments. It will also be appreciated that many modifications and variations will be apparent to those skilled in the art without departing from the scope of the invention.

10: Reactor
20: Vacuum pump
110: first container
112: first functional particle
114: First functional particle whose surface property is changed
210: Second container
212: Functional solution
214: Steam
310: Third container
312: Photocurable resin

Claims (11)

Preparing first functional particles and second functional particles having the same surface characteristics;
Coupling a functionalized molecule having a functional group to the first functional particles to convert the surface characteristics of the first functional particles; And
And dispersing the second functional particles having the same surface characteristics as those of the first functional particles before the surface characteristics are converted and the first functional particles converted in surface characteristics into the photocurable resin, ≪ / RTI >
The method according to claim 1,
When the photocurable resin is hydrophilic,
The surface characteristics of the first functional particles and the second functional particles are hydrophobic,
The surface characteristic of the first functional particle is converted into hydrophilic property by the functional molecule,
Wherein the hydrophilic first functional particles and the hydrophobic second functional particles are dispersed in the photo-curable resin.
The method according to claim 1,
The step of binding the functional molecule to the functional particle includes:
Preparing a functionalized solution having the functional particle and the functional molecule in a reactor; And
And evaporating the functional solution to bond the functional molecule to the functional particle.
The method of claim 3,
The step of preparing the functional particles in the reactor comprises:
Preparing a first phosphor emitting light in a first wavelength band and a second phosphor emitting light in a second wavelength band in the reactor,
Wherein the step of bonding the functional molecule to the functional particle comprises:
And bonding the first phosphor and the second phosphor to the functional molecule.
The method according to claim 1,
When the photocurable resin is hydrophobic,
The surface characteristics of the first functional particles and the second functional particles are hydrophilic,
The surface characteristic of the first functional particle is converted into a hydrophobic property by the functional molecule,
Wherein the hydrophobic first functional grains and the hydrophilic second functional grains are dispersed in the photocurable resin.
The method according to claim 1,
Wherein the first functional particles and the second functional particles each include a first phosphor and a second phosphor that emit different lights.
The method according to claim 1,
Wherein a dispersion degree of the first functional particles and a dispersion of the second functional particles in the photocurable resin are different from each other.
delete Photocurable resin;
A first functional particle dispersed in the photocurable resin and bonded to the functional molecule having a functional group to have the same surface characteristics as the photocurable resin; And
And a second functional particle dispersed in the photo-curing resin and having a surface property different from that of the photo-curable resin, at a lower dispersion than the first functional particle.
10. The method of claim 9,
Wherein the first functional particles and the second functional particles each include a first phosphor and a second fluorescent material,
Wherein the first phosphor and the second phosphor react with light of the same wavelength band, and emit light of different wavelength bands.
A structure manufactured by a three-dimensional printing process using the three-dimensional printing composite material according to any one of claims 9 to 10,
Wherein the first functional particles are uniformly distributed in the structure,
Wherein the second functional particles are concentrated in a portion of the structure.
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