KR102391727B1 - Silicon compound and method for producing the same - Google Patents

Abstract

The present invention relates to a silicone compound, and can be used as a photocurable polymer through acrylate and/or epoxidation of a silicone polymer. The silicon compound may be used as a material for 3D printing of the SLA method.

Description

Silicone compound and manufacturing method thereof

The present invention relates to a silicone compound and a method for preparing the same. Specifically, it relates to a silicone compound that can be used as a material for UV curing by acrylated and/or epoxidized through a modification reaction of silicone oil.

A 3D printer is an equipment that can produce a real three-dimensional shape as it is based on an input three-dimensional drawing, just like printing type or picture. Recently, 3D printing technology has become a central issue leading the 4th industrial revolution, and is widely used for making various models such as automobiles, medical care, art, and education fields. The principle of 3D printers can be largely divided into cutting type and stacking type, and most of the 3D printers that are actually applied fall into the layered type without loss of material. Methods using the layered principle include Stereo Lithography Apparatus (SLA), Fused Deposition Modeling (FDM), fused Filament Fabrication (FFF), and Selective Laser Sintering (SLS).

SLA is a method of molding by projecting a laser beam into a tank containing a liquid photocurable resin, and an epoxy-type photopolymer, which is a photocurable resin, is mainly used. FDM is formed in three dimensions while the input filamentary material is discharged in a molten state from the nozzle of the printer moving in the x, y, and z axes, and thermoplastic plastic is used as the main material. SLS implements 3D printing by selectively sintering by firing a laser into a water tank containing powdery materials such as metal, plastic, and ceramic powder.

In particular, in order to perform 3D printing using the SLA method, it is necessary to use a photocurable resin such as UV curing. In order to have photocuring properties, it must have a functional group such as acrylic or epoxy.

On the other hand, since silicone is harmless to the human body, it can be variously applied to biomedical, educational, industrial, and the like. Research is being conducted to use such a silicon material as a material for 3D printing.

Korean Patent Publication No. KP 10-2010-0073033

The present application relates to a silicone compound for solving the problems of the prior art described above, and may be used as a photocurable polymer through acrylate and/or epoxidation of a silicone polymer. The silicon compound may be used as a material for 3D printing of the SLA method.

In addition, a second object of the present invention relates to a method for producing a silicone compound, and by using a reforming reaction rather than a polymerization reaction, it is easy to simplify the process and reduce the cost.

In addition, a third object of the present invention is to provide an artificial ear including the silicon compound, and the artificial ear may include graphene to increase sensitivity to vibration.

The silicone compound of the present invention for achieving the above technical problem is characterized in that it is represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ , R ₅ , R ₆ , and R ₁₀ are each independently optionally substituted linear or branched C ₁ -C ₂₀ alkyl, which may be substituted C ₆ -C ₂₀ aryl , O, Si, S, H, F, Cl, Br, I and a material selected from the group consisting of combinations thereof, wherein R ₂ , R ₃ , R ₄ , R ₇ , R ₈ and R ₉ are each independently linear or branched C ₁ -C ₂₀ alkyl that may be substituted with, wherein the substitution is C ₁ -C ₆ alkyl, C ₆ -C ₂₀ aryl, O, Si, S, H, F, Cl, Br , I and combinations thereof are substituted by a material selected from the group consisting of, and m, n, x and z may each independently be an integer of 1 to 1,000, but is not limited thereto.

The silicone compound may include a compound represented by the following Chemical Formula 2, but is not limited thereto.

[Formula 2]

In Formula 2, R ₁ and R ₁₀ are each independently optionally substituted linear or branched C ₁ -C ₂₀ alkyl, optionally substituted C ₆ -C ₂₀ aryl, O, Si, S, H, F, Cl, Br, I and a material selected from the group consisting of combinations thereof, wherein R ₂ , R ₃ , R ₄ , R ₇ , R ₈ and R ₉ are each independently linear or minute which may be substituted topography C ₁ -C ₂₀ alkyl, wherein the substitution is C ₁ -C ₆ alkyl, C ₆ -C ₂₀ aryl, O, Si, S, H, F, Cl, Br, I and combinations thereof It is to be substituted by a material selected from the group consisting of, and m, n, x and z may each independently be an integer of 1 to 1,000, but is not limited thereto.

The R ₁ , R ₆ , and R ₁₀ may each independently be an alkyl group including a functional group selected from the group consisting of an epoxy group, an acrylo group, a hydroxyl group, an ether group, and combinations thereof, but is not limited thereto. .

The silicone compound may be cured within 60 seconds when irradiated with ultraviolet rays after mixing with a photoinitiator, but is not limited thereto.

The method for preparing a silicone compound of the present application includes preparing a mixture by mixing a compound represented by the following Chemical Formula 3, acrylic acid, a first solvent, and a catalyst; dissolving the mixture by heat treatment; extracting the dissolved mixture using a second solvent; and distilling the solvent of the extracted mixture.

[Formula 3]

In Formula 3, R ₁ , R ₆ , and R ₁₀ are each independently optionally substituted linear or branched C ₁ -C ₂₀ alkyl, optionally substituted C ₆ -C ₂₀ aryl, O, Si, S, H, F, Cl, Br, I and a material selected from the group consisting of combinations thereof, wherein R ₂ , R ₃ , R ₇ , R ₈ and R ₉ are each independently linear or branched C ₁ -C ₂₀ alkyl, wherein the substitution is C ₁ -C ₆ alkyl, C ₆ -C ₂₀ aryl, O, Si, S, H, F, Cl, Br, I and combinations thereof It is to be substituted by a material selected from the group consisting of, and x, y and z may each independently be an integer of 1 to 1,000, but is not limited thereto.

The compound represented by Formula 3 may include a compound represented by Formula 4 below, but is not limited thereto.

[Formula 4]

R ₁ and R ₁₀ are each independently optionally substituted linear or branched C ₁ -C ₂₀ alkyl, optionally substituted C ₆ -C ₂₀ aryl, O, Si, S, H, F, Cl , Br, I, and a material selected from the group consisting of combinations thereof, wherein R ₂ , R ₃ , R ₇ , R ₈ and R ₉ are each independently a linear or branched C ₁ -C ₂₀ that may be substituted alkyl, and the substitution is by a material selected from the group consisting of C ₁ -C ₆ alkyl, C ₆ -C ₂₀ aryl, O, Si, S, H, F, Cl, Br, I and combinations thereof. It is to be substituted, and x, y and z may each independently be an integer of 1 to 1,000, but is not limited thereto.

The R ₁ , R ₆ , and R ₁₀ may each independently be an alkyl group including a functional group selected from the group consisting of an epoxy group, an acrylo group, a hydroxyl group, an ether group, and combinations thereof, but is not limited thereto. .

The first solvent and the second solvent are each independently toluene, dichloromethane, tetrahydrofuran, acetonitrile, ethanol, methanol, ethyl ether, acetone, isopropyl alcohol, benzene, xylene, N-methylpyridone, Nitrobenzene, dimethylformamide, dimethyl sulfoxide, diethyl carbonate, benzyl acetate, dimethyl glutarate, ethyl acetoacetate, isobutyl isobutanoate, isobutyl acetate, dioxane, methyl ethyl ketone, meta-cresol and a solvent selected from the group consisting of combinations thereof, but is not limited thereto.

The catalyst may include a material selected from the group consisting of triethylene amine, trimethylamine, trimethylamine, ammonia, dimethylamine, methylamine, and combinations thereof. It is not limited.

The composition for 3D printing of the present application includes a silicone compound represented by Chemical Formula 1; graphene; and a photoinitiator.

The silicone compound may include a compound represented by the following Chemical Formula 2, but is not limited thereto.

Based on 100 parts by weight of the silicon compound, the graphene may include 0.05 parts by weight to 0.50 parts by weight, but is not limited thereto.

The artificial ear of the present application is a silicone compound represented by Formula 1; graphene; and a photoinitiator; may be included.

Based on 100 parts by weight of the silicon compound, the graphene may include 0.05 parts by weight to 0.50 parts by weight, but is not limited thereto.

The above-described problem solving means are merely exemplary, and should not be construed as limiting the present application. In addition to the exemplary embodiments described above, additional embodiments may exist in the drawings and detailed description.

The disclosed technology may have the following effects. However, this does not mean that a specific embodiment should include all of the following effects or only the following effects, so the scope of the disclosed technology should not be understood as being limited thereby.

According to the above-described problem solving means of the present application, the silicone compound according to the present application includes an acryl group and/or an epoxy group. Since it contains the acrylic group and the epoxy group, it can be used as a photocurable polymer such as UV curing. In particular, the silicone compound may be used as a material for 3D printing of the SLA method.

In addition, the silicone compound may be prepared through a modification reaction of a silicone polymer, but is not limited thereto. In general, the process of modifying the polymer is simpler than that of synthesizing the polymer through polymerization of the monomer. In addition, a functional group to be modified may be selectively substituted through a modification reaction.

Furthermore, the artificial ear of the present application increases the sensitivity to detect vibration by adding the graphene. Accordingly, the minimum audible decibel (dB) may be lowered when the artificial ear is used. That is, by using the artificial ear, a small sound can be heard better.

The preparation method of the diaryl amine compound can synthesize the diaryl amine compound without using a transition metal. Specifically, benzine (Compound 1) and isocyanate (Compound 2) react to synthesize a diaryl amine compound, which has the advantage of exhibiting high yield and good regioselectivity. It is economical because it synthesizes a diarylamine compound without using an expensive transition metal.

In addition, the method for preparing the diaryl amine compound according to the present application is economical because additional reaction reagents such as water and base are not required in the synthesis process.

Furthermore, various diaryl amine compounds can be prepared by adjusting the functional groups of benzine and isocyanate according to the diaryl amine compound to be synthesized.

1 is a flowchart of a method for manufacturing a silicone compound according to an embodiment of the present application.
2 (a) and (b) are FT-IR (Fourier Transform Infrared spectroscopy) graphs of the silicon compound prepared according to an embodiment of the present application.
Figure 3a is a NMR (nuclear magnetic resonance) graph of the silicone compound prepared according to an embodiment of the present application, Figure 3b is a NMR (nuclear magnetic resonance) graph of the epoxy silicone oil.
4 (a) and (b) are FT-IR (Fourier Transform Infrared spectroscopy) graphs of the silicon compound prepared according to the comparative example of the present application.
5A is a NMR (nuclear magnetic resonance) graph of a hydroxyl vinyl silicone oil, and FIG. 5B is a NMR (nuclear magnetic resonance) graph of a silicone compound prepared according to a comparative example of the present application.
6 is a photograph when the UV curing experiment of the silicone compound prepared according to the present example is performed.
7 is a photograph when an ultraviolet curing experiment of epoxy silicone oil is performed as a comparative example.
8 is a photograph when an ultraviolet curing experiment of a silicone compound prepared according to a comparative example is performed.
9 is a photograph of a UV curing experiment of hydroxyl vinyl silicone oil as a comparative example.
Figure 10a is a graph showing the amount of acetone extraction according to the time during which the post-curing of the silicone compound prepared according to the present Example is performed, and Figure 10b is the cross-linking according to the time of the post-curing of the silicone compound prepared according to the present embodiment This is a graph showing the density.
11 is a photograph of a 3D printed printed ear prepared with the silicone compound prepared according to this embodiment.
12 is a photograph of a 3D printed printed ear prepared with a silicone compound prepared according to this comparative example.
13A is a graph showing the tensile strength according to the amount of graphene of the silicon compound prepared according to the present embodiment, and FIG. 13B is a graph measuring the elongation according to the amount of graphene of the silicon compound prepared according to the present embodiment.
14 is a graph showing the electrical resistance according to the amount of graphene of the silicon compound prepared according to the present embodiment.
15 is a graph showing the thermal conductivity according to the amount of graphene of the silicon compound prepared according to the present embodiment.
16 is a photograph of a 3D printed ear prepared with the silicone compound prepared according to this embodiment.
17 is a graph showing the voltage change according to time of the artificial ear manufactured according to the present embodiment.

Since the present invention can have various changes and can have various embodiments, specific embodiments are illustrated in the drawings and will be described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

In describing each figure, like reference numerals are used for like elements. Terms such as first, second, etc. may be used to describe various elements, but the elements should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another.

For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component. The term “and/or” includes a combination of a plurality of related listed items or any of a plurality of related listed items.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

Terms such as those defined in commonly used dictionaries should be interpreted as having meanings consistent with the meanings in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. shouldn't

Throughout this specification, when a member is positioned “on”, “on”, “on”, “on”, “under”, “under”, or “under” another member, this means that a member is positioned on the other member. It includes not only the case where they are in contact, but also the case where another member exists between two members.

Throughout this specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

As used herein, the terms "about," "substantially," and the like are used in a sense at or close to the numerical value when the manufacturing and material tolerances inherent in the stated meaning are presented, and to aid in the understanding of the present application. It is used to prevent an unconscionable infringer from using the mentioned disclosure in an unreasonable way. Also, throughout this specification, "step to" or "step to" does not mean "step for".

Throughout this specification, the term "combination of these" included in the expression of the Markush form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the Markush form, and the components It is meant to include one or more selected from the group consisting of.

Throughout this specification, reference to “A and/or B” means “A or B”, or “A and B”.

Throughout this specification, the term "aromatic ring" refers to a C _6-30 aromatic hydrocarbon ring group, for example, phenyl, naphthyl, biphenyl, terphenyl, fluorene, phenanthrenyl, triphenylenyl, perylenyl , chrysenyl, fluoranthenyl, benzofluorenyl, benzotriphenylenyl, benzochrysenyl, anthracenyl, stilbenyl, means including an aromatic ring such as pyrenyl, "aromatic heterocyclic ring" is at least one As an aromatic ring containing a hetero element, for example, pyrrolyl, pyrazinyl, pyridinyl, indolyl, isoindolyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, quinolyl group, isoquinolyl, quinoxalinyl, carbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, thienyl, and pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, Indole ring, quinoline ring, acridine ring, pyrrolidine ring, dioxane ring, piperidine ring, morpholine ring, piperazine ring, carbazole ring, furan ring, thiophene ring, oxazole ring, oxadia Contains an aromatic heterocyclic group formed from a azole ring, a benzoxazole ring, a thiazole ring, a thiadiazole ring, a benzothiazole ring, a triazole ring, an imidazole ring, a benzoimidazole ring, a pyran ring, and a dibenzofuran ring means to do

Throughout this specification, the term "fused", with respect to two or more rings, means that at least one pair of adjacent atoms is included in both rings.

Throughout this specification, the term “alkyl” may include linear or branched, saturated or unsaturated C ₁ -C ₆ alkyl, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl or their It may include all possible isomers, but may not be limited thereto.

Hereinafter, the silicone compound of the present application and a method for manufacturing the same will be described in detail with reference to embodiments, examples, and drawings. However, the present application is not limited to these embodiments and examples and drawings.

The present application relates to a silicone compound represented by the following formula (1).

In Formula 1, R ₁ , R ₅ , R ₆ , and R ₁₀ are each independently optionally substituted linear or branched C ₁ -C ₂₀ alkyl, which may be substituted C ₆ -C ₂₀ aryl , O, Si, S, H, F, Cl, Br, I and a material selected from the group consisting of combinations thereof, wherein R ₂ , R ₃ , R ₄ , R ₇ , R ₈ and R ₉ are each independently linear or branched C ₁ -C ₂₀ alkyl that may be substituted with, wherein the substitution is C ₁ -C ₆ alkyl, C ₆ -C ₂₀ aryl, O, Si, S, H, F, Cl, Br , I and combinations thereof are substituted by a material selected from the group consisting of, and m, n, x and z may each independently be an integer of 1 to 1,000, but is not limited thereto.

The silicone compound may include a compound represented by the following Chemical Formula 2, but is not limited thereto.

In Formula 2, R ₁ and R ₁₀ are each independently optionally substituted linear or branched C ₁ -C ₂₀ alkyl, optionally substituted C ₆ -C ₂₀ aryl, O, Si, S, H, F, Cl, Br, I and a material selected from the group consisting of combinations thereof, wherein R ₂ , R ₃ , R ₄ , R ₇ , R ₈ and R ₉ are each independently linear or minute which may be substituted topography C ₁ -C ₂₀ alkyl, wherein the substitution is C ₁ -C ₆ alkyl, C ₆ -C ₂₀ aryl, O, Si, S, H, F, Cl, Br, I and combinations thereof It is to be substituted by a material selected from the group consisting of, and m, n, x and z may each independently be an integer of 1 to 1,000, but is not limited thereto.

The R ₁ , R ₆ , and R ₁₀ may each independently be an alkyl group including a functional group selected from the group consisting of an epoxy group, an acrylo group, a hydroxyl group, an ether group, and combinations thereof, but is not limited thereto. .

The silicone compound may include a compound represented by the following Chemical Formula 5, but is not limited thereto.

The silicone compound may include a compound represented by the following Chemical Formula 6, but is not limited thereto.

In Formulas 5 and 6, R ₂ , R ₃ , R ₄ , R ₇ , R ₈ and R ₉ are each independently a linear or branched C ₁ -C ₂₀ alkyl that may be substituted, and the substitution is C ₁ -C ₆ Alkyl, C ₆ -C ₂₀ Aryl, O, Si, S, H, F, Cl, Br, I and combinations thereof are substituted by a material selected from the group consisting of, wherein m, n, x and z may each independently be an integer of 1 to 1,000, but is not limited thereto.

The silicone compound may be cured within 60 seconds when irradiated with ultraviolet rays after mixing with a photoinitiator, but is not limited thereto.

The silicone compound according to the present application includes an acryl group and/or an epoxy group. Since it contains the acrylic group and the epoxy group, it can be used as a photocurable polymer such as UV curing. In particular, the silicone compound may be used as a material for 3D printing of the SLA method.

The m+n may be greater than x+z, but is not limited thereto.

When the number m of silicone substituted with the acryl group and the number n of silicone substituted with the epoxy group are greater than the number of silicones unsubstituted with the acryl group or the epoxy group, the silicone compound undergoes photocuring, The hardness may be greater, but is not limited thereto.

On the other hand, in the case of a silicone polymer, when only both ends are substituted with an acryl group and/or an epoxy group, photocuring may be achieved, but hardness may be low.

The silicone compound may be prepared through a modification reaction of a silicone polymer, but is not limited thereto. In general, the process of modifying the polymer is simpler than that of synthesizing the polymer through polymerization of the monomer. In addition, a functional group to be modified may be selectively substituted through a modification reaction.

The present application includes the steps of preparing a mixture by mixing a compound represented by the following Chemical Formula 3, acrylic acid, a first solvent, and a catalyst; dissolving the mixture by heat treatment; extracting the dissolved mixture using a second solvent; And distilling the solvent of the extracted mixture; relates to a method for producing a silicone compound comprising a.

In Formula 3, R ₁ , R ₆ , and R ₁₀ are each independently optionally substituted linear or branched C ₁ -C ₂₀ alkyl, optionally substituted C ₆ -C ₂₀ aryl, O, Si, S, H, F, Cl, Br, I and a material selected from the group consisting of combinations thereof, wherein R ₂ , R ₃ , R ₇ , R ₈ and R ₉ are each independently linear or branched C ₁ -C ₂₀ alkyl, wherein the substitution is C ₁ -C ₆ alkyl, C ₆ -C ₂₀ aryl, O, Si, S, H, F, Cl, Br, I and combinations thereof It is to be substituted by a material selected from the group consisting of, and x, y and z may each independently be an integer of 1 to 1,000, but is not limited thereto.

1 is a flowchart of a method for manufacturing a silicone compound according to an embodiment of the present application.

First, a mixture is prepared by mixing the compound represented by Chemical Formula 1, acrylic acid, a first solvent, and a catalyst (S100).

The compound represented by Formula 3 may include a compound represented by Formula 4 below, but is not limited thereto.

R ₁ and R ₁₀ are each independently optionally substituted linear or branched C ₁ -C ₂₀ alkyl, optionally substituted C ₆ -C ₂₀ aryl, O, Si, S, H, F, Cl , Br, I, and a material selected from the group consisting of combinations thereof, wherein R ₂ , R ₃ , R ₇ , R ₈ and R ₉ are each independently a linear or branched C ₁ -C ₂₀ that may be substituted alkyl, and the substitution is by a material selected from the group consisting of C ₁ -C ₆ alkyl, C ₆ -C ₂₀ aryl, O, Si, S, H, F, Cl, Br, I and combinations thereof. It is to be substituted, and x, y and z may each independently be an integer of 1 to 1,000, but is not limited thereto.

The R ₁ , R ₆ , and R ₁₀ may each independently be an alkyl group including a functional group selected from the group consisting of an epoxy group, an acrylo group, a hydroxyl group, an ether group, and combinations thereof, but is not limited thereto. .

The compound represented by Formula 3 may include, but is not limited to, epoxy silicone oil.

The epoxy group of Formula 4 may be acrylated by reacting with the acrylic acid, but is not limited thereto.

The acrylic acid and the compound represented by Formula 3 may be mixed in a weight ratio of 1:2 to 1:10, but is not limited thereto.

When the weight ratio of the acrylic acid and the compound represented by Chemical Formula 3 is less than 1:2 or more than 1:10, the photocuring property may not be properly expressed because the reforming reaction does not sufficiently occur.

The first solvent is toluene, dichloromethane, tetrahydrofuran, acetonitrile, ethanol, methanol, ethyl ether, acetone, isopropyl alcohol, benzene, xylene, N-methylpyridone, nitrobenzene, dimethylformamide, dimethyl group consisting of sulfoxide, diethyl carbonate, benzyl acetate, dimethyl glutarate, ethylacetoacetate, isobutyl isobutanoate, isobutyl acetate, dioxane, methylethylketone, meta-cresol and combinations thereof It may include a solvent selected from, but is not limited thereto.

The catalyst may include a material selected from the group consisting of triethylene amine, trimethylamine, trimethylamine, ammonia, dimethylamine, methylamine, and combinations thereof. It is not limited.

Then, the mixture is dissolved by heat treatment (S200).

The heat treatment may be performed at a temperature of 60° C. to 200° C., but is not limited thereto.

The heat treatment may be performed for 1 hour to 12 hours, but is not limited thereto.

The temperature and time of the heat treatment may be adjusted according to the type of the mixture, and may be to appropriately control the conditions under which all substances can be dissolved in the first solvent.

Then, the dissolved mixture is extracted using a second solvent (S300).

The second solvent is toluene, dichloromethane, tetrahydrofuran, acetonitrile, ethanol, methanol, ethyl ether, acetone, isopropyl alcohol, benzene, xylene, N-methylpyridone, nitrobenzene, dimethylformamide, dimethyl group consisting of sulfoxide, diethyl carbonate, benzyl acetate, dimethyl glutarate, ethylacetoacetate, isobutyl isobutanoate, isobutyl acetate, dioxane, methylethylketone, meta-cresol and combinations thereof It may include a solvent selected from, but is not limited thereto.

The second solvent may be the same as or different from the first solvent.

The second solvent may be preferably dichloromethane, but is not limited thereto.

It may further include the step of washing the extracted mixture.

The washing step may be washing the mixture with sodium carbonate solution, but is not limited thereto.

Then, the solvent of the extracted mixture is distilled (S400).

The distilling step is for removing the first solvent and/or the second solvent, and may be heating to a temperature higher than the boiling point of the first solvent and/or the second solvent, but is not limited thereto.

After distilling the solvent, the silicone compound represented by Formula 1 may be obtained.

The manufacturing method of the silicone compound of the present application is easy to simplify and reduce the cost by using a reforming reaction rather than a polymerization reaction.

The present application is a silicone compound represented by Formula 1; graphene; And a photoinitiator; relates to a composition for 3D printing comprising.

The silicone compound may include a compound represented by the following Chemical Formula 2, but is not limited thereto.

Based on 100 parts by weight of the silicon compound, the graphene may include 0.05 parts by weight to 0.50 parts by weight, but is not limited thereto.

The composition for 3D printing can be used as a material for artificial intelligence by including the graphene to improve durability and increase electrical conductivity at the same time.

The photoinitiator is 2,4,6-trimethylbenzoyl diphenyl phosphine, 2,2-diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy- Cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl) )-Benzyl]-phenyl}-2-methylpropan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, and combinations thereof It may include a material selected from, but is not limited thereto.

The photoinitiator may act to initiate a reaction by absorbing ultraviolet rays to generate free radicals.

The composition for 3D printing may further include a diluent, but is not limited thereto.

The diluent may be used for the purpose of lowering the viscosity of the photocurable composition.

The diluent may include a material selected from the group consisting of hydroxy ethyl acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylol propane triacrylate, and combinations thereof, but is limited thereto. it is not going to be

The diluent may be 1 part by weight to 30 parts by weight based on 100 parts by weight of the composition for 3D printing, but is not limited thereto.

When the diluent is less than 1 part by weight based on 100 parts by weight of the composition for 3D printing, there is little dilution effect and the composition for 3D printing may have a high viscosity. In addition, when the diluent is more than 30 parts by weight, flexibility may decrease and shrinkage of the cured layer may occur.

The present application is a silicone compound represented by Formula 1; graphene; And it relates to an artificial ear comprising; and a photoinitiator.

Based on 100 parts by weight of the silicon compound, the graphene may include 0.05 parts by weight to 0.50 parts by weight, but is not limited thereto.

The artificial ear increases the sensitivity for detecting vibration by adding the graphene. Accordingly, the minimum audible decibel (dB) may be lowered when the artificial ear is used. That is, by using the artificial ear, a small sound can be heard better.

When the amount of graphene is less than 0.05 parts by weight based on 100 parts by weight of the silicone compound, the sensitivity of the artificial ear may not be sufficiently increased. In addition, when the graphene content exceeds 0.50 parts by weight, the price may increase.

The present invention will be described in more detail through the following examples, but the following examples are for illustrative purposes only and are not intended to limit the scope of the present application.

First, epoxy silicone oil (ES) and acrylic acid were mixed in a reaction vessel at a weight ratio of 6:1, and triethylamine and toluene were added and dissolved at a temperature of 110° C. for 8 hours. Then, the mixture was extracted using dichloromethane. The extracted mixture was washed with water and sodium carbonate solution. The solvent of the washed mixture was distilled to obtain an acrylated silicone compound.

A silicon compound including graphene was obtained in the same manner as in Example 1, except that 0.05 parts by weight of graphene was added to the mixture.

A silicon compound including graphene was obtained in the same manner as in Example 1, except that 0.07 parts by weight of graphene was added to the mixture.

A silicon compound including graphene was obtained in the same manner as in Example 1, except that 0.10 parts by weight of graphene was added to the mixture.

A silicon compound including graphene was obtained in the same manner as in Example 1, except that 0.30 parts by weight of graphene was added to the mixture.

[Comparative Example 1]

First, hydroxyl vinyl silicone oil (HS) and acrylic acid were mixed in a weight ratio of 6:1 in a reaction vessel, and sulfuric acid was added thereto and dissolved at a temperature of 60° C. for 7 hours. Then, the mixture was extracted using dichloromethane. The extracted mixture was washed with water and sodium carbonate solution. The solvent of the washed mixture was distilled to obtain an acrylated silicone compound.

[evaluation]

One. Analysis for Identification of Silicone Compounds

An analysis was performed on whether the reforming reaction of the silicone compound prepared in Example 1 and Comparative Example 1 was properly performed, and the results are shown in FIGS. 2 to 5 .

2 (a) and (b) are FT-IR (Fourier Transform Infrared spectroscopy) graphs of the silicon compound prepared according to an embodiment of the present application.

Specifically, (a) of FIG. 2 is an FT-IR graph of wavenumbers of 500 cm-1 to 4,000 cm-1, and FIG. 2(b) is an FT-IR graph of wavenumbers of 800 cm-1 to 1,800 cm-1. .

According to the results shown in FIG. 2, in the FT-IR results of the acrylated silicone compound of Example 1, the epoxy group peak at 910 cm ^-1 disappeared, and 1,732 cm ^-1 (C=O), 1,634 cm ^-1 and 1,620 It can be seen that cm ^-1 (C=C of the acryl group) and 1,198 cm ^-1 (CO-OC) peaks appear.

Figure 3a is a NMR (nuclear magnetic resonance) graph of the silicone compound prepared according to an embodiment of the present application, Figure 3b is a NMR (nuclear magnetic resonance) graph of the epoxy silicone oil.

According to the results shown in FIGS. 3a and 3b, the peaks shown at 3.86 ppm to 4.01 ppm, 4.40 ppm to 4.46 ppm, 2.60 ppm to 2.87 ppm, and 3.15 ppm to 3.24 ppm corresponding to the epoxy group of FIG. 3b disappear in FIG. 3a, It can be seen that peaks appear at 5.21 ppm and 6.0 ppm, which correspond to the acrylic ester group.

4 (a) and (b) are FT-IR (Fourier Transform Infrared spectroscopy) graphs of the silicon compound prepared according to the comparative example of the present application.

Specifically, (a) of FIG. 4 is an FT-IR graph of wavenumbers of 500 cm-1 to 4,000 cm-1, and FIG. 4(b) is an FT-IR graph of wavenumbers of 800 cm-1 to 1,800 cm-1. .

According to the results shown in FIG. 4, in the FT-IR result of the acrylated silicone compound of Comparative Example 1, the Si-OH peak at 3,273 cm ^-1 disappeared, and 1,700 cm ^-1 (C=O), 1,634 cm ^-1 and It can be seen that 1,620 cm ^-1 (C=C of the acryl group) and 1,214 cm ^-1 (CO-OC) peaks appear.

5A is a NMR (nuclear magnetic resonance) graph of a hydroxyl vinyl silicone oil, and FIG. 5B is a NMR (nuclear magnetic resonance) graph of a silicone compound prepared according to a comparative example of the present application.

According to the results shown in FIGS. 5A and 5B, it can be seen that the 2.5 ppm peak corresponding to the hydroxyl group of FIG. 5A disappears in FIG. 5B, and the peak appears at 5.21 ppm corresponding to the acrylic ester group.

2. UV curing of silicone compounds

The UV curing experiment of the silicone compound prepared in Example 1 and Comparative Example 1 was performed, and the results are shown in FIGS. 6 to 12 .

The silicone compound prepared in Example 1 was irradiated with a UV lamp (200 mW) with a wavelength of 405 nm to a material in which 1 part by weight of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide was mixed, and the results are shown in Fig. 6 was shown.

6 is a photograph when the UV curing experiment of the silicone compound prepared according to the present example is performed.

Specifically, FIG. 6 is a photograph when the UV lamp is irradiated for less than 1 second.

A material obtained by mixing 1 part by weight of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide in epoxy silicone oil was irradiated with a UV lamp (200 mW) with a wavelength of 405 nm, and the results are shown in FIG. 7 .

7 is a photograph when an ultraviolet curing experiment of epoxy silicone oil is performed as a comparative example.

Specifically, FIG. 7 is a photograph when the UV lamp is irradiated for more than 120 seconds.

According to the results shown in FIGS. 6 and 7, the silicone compound prepared according to the example hardens when irradiated with ultraviolet rays after mixing with the photoinitiator, whereas the epoxy silicone oil is mixed with the photoinitiator and then irradiated with ultraviolet rays. It can be confirmed that it does not harden even when irradiated for a while.

That is, it can be confirmed that the silicone compound prepared through the acrylate modification reaction according to the present embodiment effectively exhibits photocurability.

A material in which 1 part by weight of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide was mixed with the silicone compound prepared in Comparative Example 1 was irradiated with a UV lamp (200 mW) with a wavelength of 405 nm, and the results are shown in Fig. 8.

8 is a photograph when an ultraviolet curing experiment of a silicone compound prepared according to a comparative example is performed.

Specifically, FIG. 8 is a photograph when the UV lamp is irradiated for less than 1 second.

A 405 nm wavelength UV lamp (200 mW) was irradiated to a material in which 1 part by weight of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide was mixed with hydroxyl vinyl silicone oil, and the result is shown in FIG. it was

9 is a photograph of a UV curing experiment of hydroxyl vinyl silicone oil as a comparative example.

Specifically, FIG. 9 is a photograph when the UV lamp is irradiated for more than 120 seconds.

According to the results shown in FIGS. 8 and 9, the silicone compound acrylated at both ends of Comparative Example 1 hardened when irradiated with ultraviolet rays after mixing with the photoinitiator, whereas the hydroxyl vinyl silicone oil was mixed with the photoinitiator and then irradiated with ultraviolet rays. , it can be confirmed that it does not harden even when irradiated for more than 2 minutes.

A material obtained by mixing 1 part by weight of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and a diluent to each of the silicone compounds prepared in Example 1 and Comparative Example 1 was prepared by SLA (Stereo Lithography Apparatus) method. Thus, an ear shape was 3D printed in a size of 50.55 mm X 64.15 mm X 18.39 mm.

After the 3D printing, post-curing was performed on the prepared ear-shaped sample, and post-curing was performed by irradiating a high voltage mercury lamp with a wavelength of 365 nm (400 W, 42 W/cm ³ ). The amount of acetone extraction and crosslinking density according to the time during which the post-curing was performed is shown in FIG. 10 .

Figure 10a is a graph showing the amount of acetone extraction according to the time during which the post-curing of the silicone compound prepared according to the present Example is performed, and Figure 10b is the cross-linking according to the time of the post-curing of the silicone compound prepared according to the present embodiment This is a graph showing the density.

According to the results shown in FIGS. 10A and 10B , an appropriate post-curing time can be determined to be about 10 seconds.

After 3D printing in the shape of an ear using the silicone compound prepared in Example 1 and Comparative Example 1, photographs of samples subjected to post-curing are shown in FIGS. 11 and 12, respectively.

11 is a photograph of a 3D printed printed ear prepared with the silicone compound prepared according to this embodiment.

12 is a photograph of a 3D printed printed ear prepared with a silicone compound prepared according to this comparative example.

According to the results shown in FIGS. 11 and 12, it can be seen that the 3D printed ear prepared with the silicone compound prepared in Comparative Example 1 appears in the form of an ear, but the shape of the 3D printed ear prepared with the silicone compound prepared in Example 1 This can be seen more clearly.

In the silicone compound of Comparative Example 1, only hydroxyl groups at both ends were acrylated, whereas in the silicone compound of Example 1, a large portion of the polymer monomer was acrylated. That is, Example 1 can be determined to be a silicone compound in which acrylation is more advanced than Comparative Example 1. As in Example 1, the silicone compound that has been further acrylated has stronger hardness and faster curing when UV curing is performed, so that 3D printing can be performed in a desired shape. However, when only both ends are acrylated as in Comparative Example 1, UV curing proceeds, but there is a limit in manufacturing an accurate three-dimensional model to be 3D printed.

3. Characteristics of Silicon Compounds Containing Graphene

A 405 nm wavelength UV lamp (200 mW) was irradiated to a material in which 1 part by weight of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide was mixed with the silicone compound prepared in Examples 1 to 5, and as a result, is shown as FIGS. 13 to 15 .

13A is a graph showing the tensile strength according to the amount of graphene of the silicon compound prepared according to the present embodiment, and FIG. 13B is a graph measuring the elongation according to the amount of graphene of the silicon compound prepared according to the present embodiment.

According to the results shown in FIGS. 13A and 13B, it can be confirmed that the tensile strength and elongation increase as the amount of mixed graphene increases.

14 is a graph showing the electrical resistance according to the amount of graphene of the silicon compound prepared according to the present embodiment.

According to the results shown in FIG. 14 , it can be confirmed that the electrical resistance decreases as the amount of mixed graphene increases. That is, it can be seen that the electrical conductivity increases as the amount of mixed graphene increases.

15 is a graph showing the thermal conductivity according to the amount of graphene of the silicon compound prepared according to the present embodiment.

According to the results shown in FIG. 15 , it can be confirmed that the thermal conductivity increases as the thickness of the mixed graphene increases.

4. Artificial ear made of silicon compound containing graphene

A material obtained by mixing 1 part by weight of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and a diluent to each of the silicone compounds prepared in Examples 1 and 4 was 50.55 using the SLA (Stereo Lithography Apparatus) method. An artificial ear was manufactured by 3D printing an ear shape with a size of mm X 64.15 mm X 18.39 mm. The characteristics of each of the artificial ears were analyzed, and are shown in FIGS. 16 and 17 .

The artificial ear is shown as FIG. 16 .

16 is a photograph of a 3D printed ear prepared with the silicone compound prepared according to this embodiment.

17 shows a voltage change with time when a sound is generated using an ultrasonic device and the sound is connected to the oscilloscope and the artificial ear.

17 is a graph showing the voltage change according to time of the artificial ear manufactured according to the present embodiment.

According to the results shown in FIG. 17 , it can be confirmed that the artificial ear made of the silicone compound prepared in Example 4 senses vibration better. That is, an artificial ear using a silicon compound including graphene can better detect a change in response to vibration, and thus better detect sound. An artificial ear made of a silicon compound containing graphene can increase performance compared to a conventional artificial ear. In addition, it can be applied to a device that amplifies sound, such as a speaker.

The foregoing description of the present application is for illustration, and those of ordinary skill in the art to which the present application pertains will understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. For example, each component described as a single type may be implemented in a dispersed form, and likewise components described as distributed may be implemented in a combined form.

The scope of the present application is indicated by the following claims rather than the above detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present application.

Claims (14)

A silicone compound represented by the following formula (2):
[Formula 2]

In Formula 2,
R ₁ and R ₁₀ are each independently optionally substituted linear or branched C ₁ -C ₂₀ alkyl, optionally substituted C ₆ -C ₂₀ aryl, O, Si, S, H, F, Cl , Br, I, and a material selected from the group consisting of combinations thereof,
Wherein R ₂ , R ₃ , R ₄ , R ₇ , R ₈ and R ₉ are each independently a linear or branched C ₁ -C ₂₀ alkyl that may be substituted,
The substitution is a material selected from the group consisting of C ₁ -C ₆ alkyl, C ₆ -C ₂₀ aryl, O, Si, S, H, F, Cl, Br, I, and combinations thereof. ,
Wherein m, n, x and z are each independently an integer of 1 to 1,000.
delete The method of claim 1,
The R ₁ , and R ₁₀ are each independently an alkyl group including a functional group selected from the group consisting of an epoxy group, an acrylo group, a hydroxyl group, an ether group, and combinations thereof, the silicone compound.
The method of claim 1,
The silicone compound will be cured within 60 seconds when irradiated with ultraviolet rays after mixing with the photoinitiator, the silicone compound.
preparing a mixture by mixing a compound represented by the following Chemical Formula 4, acrylic acid, a first solvent, and a catalyst;
dissolving the mixture by heat treatment;
extracting the dissolved mixture using a second solvent; and
Distilling the solvent of the extracted mixture; Containing, Method for producing a silicone compound:
[Formula 4]

In Formula 4,
R ₁ and R ₁₀ are each independently optionally substituted linear or branched C ₁ -C ₂₀ alkyl, optionally substituted C ₆ -C ₂₀ aryl, O, Si, S, H, F, Cl , Br, I, and a material selected from the group consisting of combinations thereof,
Wherein R ₂ , R ₃ , R ₇ , R ₈ and R ₉ are each independently a linear or branched C ₁ -C ₂₀ alkyl that may be substituted,
The substitution is a material selected from the group consisting of C ₁ -C ₆ alkyl, C ₆ -C ₂₀ aryl, O, Si, S, H, F, Cl, Br, I, and combinations thereof. ,
Wherein x, y and z are each independently an integer of 1 to 1,000.
delete 6. The method of claim 5,
The R ₁ , and R ₁₀ are each independently an alkyl group including a functional group selected from the group consisting of an epoxy group, an acrylo group, a hydroxyl group, an ether group, and combinations thereof.
6. The method of claim 5,
The first solvent and the second solvent are each independently toluene, dichloromethane, tetrahydrofuran, acetonitrile, ethanol, methanol, ethyl ether, acetone, isopropyl alcohol, benzene, xylene, N-methylpyridone, Nitrobenzene, dimethylformamide, dimethyl sulfoxide, diethyl carbonate, benzyl acetate, dimethyl glutarate, ethyl acetoacetate, isobutyl isobutanoate, isobutyl acetate, dioxane, methyl ethyl ketone, meta-cresol And a method for producing a silicone compound comprising a solvent selected from the group consisting of combinations thereof.
6. The method of claim 5,
The catalyst is a silicone compound comprising a material selected from the group consisting of triethylene amine, triethylamine, trimethylamine, ammonia, dimethylamine, methylamine, and combinations thereof. manufacturing method.
A silicone compound represented by the following formula (2);
graphene; and
A photoinitiator; comprising, a composition for 3D printing:
[Formula 2]

In Formula 2,
R ₁ and R ₁₀ are each independently optionally substituted linear or branched C ₁ -C ₂₀ alkyl, optionally substituted C ₆ -C ₂₀ aryl, O, Si, S, H, F, Cl , Br, I, and a material selected from the group consisting of combinations thereof,
Wherein R ₂ , R ₃ , R ₄ , R ₇ , R ₈ and R ₉ are each independently a linear or branched C ₁ -C ₂₀ alkyl that may be substituted,
The substitution is a material selected from the group consisting of C ₁ -C ₆ alkyl, C ₆ -C ₂₀ aryl, O, Si, S, H, F, Cl, Br, I, and combinations thereof. ,
Wherein m, n, x and z are each independently an integer of 1 to 1,000.
delete 11. The method of claim 10,
Based on 100 parts by weight of the silicone compound, the graphene comprises 0.05 parts by weight to 0.50 parts by weight, the composition for 3D printing.
An artificial ear represented by the following formula (2), comprising a silicone compound, graphene, and a photoinitiator:
[Formula 2]

In Formula 2,
R ₁ and R ₁₀ are each independently optionally substituted linear or branched C ₁ -C ₂₀ alkyl, optionally substituted C ₆ -C ₂₀ aryl, O, Si, S, H, F, Cl , Br, I, and a material selected from the group consisting of combinations thereof,
Wherein R ₂ , R ₃ , R ₄ , R ₇ , R ₈ and R ₉ are each independently a linear or branched C ₁ -C ₂₀ alkyl that may be substituted,
The substitution is a material selected from the group consisting of C ₁ -C ₆ alkyl, C ₆ -C ₂₀ aryl, O, Si, S, H, F, Cl, Br, I, and combinations thereof. ,
Wherein m, n, x and z are each independently an integer of 1 to 1,000.
14. The method of claim 13,
Based on 100 parts by weight of the silicone compound, the graphene is an artificial ear comprising 0.05 parts by weight to 0.50 parts by weight.

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