KR20190002029A - Mechanochromic Photonic Crystal Complex comprising Non close-Packed Photonic Crystal structure - Google Patents

Abstract

The present invention relates to a mechanochromic photonic crystal composite including a non-contact photonic crystal structure and, more specifically, to a mechanochromic photonic crystal film. According to the present invention, the mechanochromic photonic crystal composite provides full-color reflective color of a visible range through elastic deformation and also has a non-contact photonic crystal structure having a sufficiently separated distance between photonic crystal particles not to provide remaining deformation after physical deformation so as to provide excellent durability after continuous use and continuously provide a constant mechanochromic effect, thereby increasing reliability about mechanochromic characteristic of the composite. Moreover, the mechanochromic photonic crystal composite provides a sensitive and correct color change even by a physical force applied to an area equal to or less than a mu;m to provide excellent precision in detection of the physical force. Accordingly, the mechanochromic photonic crystal composite including the non-contact photonic crystal structure is able to be usefully applied to fingerprint recognition and the like. According to the present invention, the mechanochromic photonic crystal composite comprises photonic crystal particles and a polymer matrix.

Description

[0001] The present invention relates to a dynamically color-changing photonic crystal composite comprising a non-contact photonic crystal structure,

The present invention relates to a dyme-discolorable photonic crystal composite comprising a non-contact photonic crystal structure.

Chameleon has an outstanding talent to quickly adjust color within a visible range. This ability is important for male-female interaction and stomach, and it has recently been revealed that chameleon uses photonic crystals to develop and change colors, not chemical pigments. The photorefractive index shows the reflection color when the modulation period of the refractive index is comparable to half of the wavelength of the visible light. In iridophores of chameleons, hard guanine nanocrystalline particles are embedded in a matrix of resilient cytoplasm to form noncontact crystals. As the cytoplasm undergoes rapid volumetric changes, lattice parameters change in the range of 240-580 nm while maintaining the lattice structure, leading to a rapid color shift across the entire visible range.

The properties of stress-induced color change or mechanochromism have been implemented using colloidal photonic crystals in a variety of applications. For example, deformation or pressure can be measured with a colorimetric system of dyed discoloration film and can be easily recognized by analyzing the color pattern of the fingerprint. Further, the light emission from the fluorescent molecule of the photonic crystal can be adjusted by the deformation of the band gap position, the color pattern can be encrypted through local modulation of the elastic modulus, and the hidden pattern is revealed when the film undergoes elongation stress .

A combination of various materials and processes has been used to mechanically discolor such colloidal crystals. For example, after filling the clearance volume of dense colloidal crystals or opal structures with elastomer, the resulting composite material exhibits color shift with deformation, but the dense colloidal crystals have a considerable rearrangement of the crystal structure due to stretching or expansion of the material Which is very limited. In addition, the deformation of such a composite material is not due to pure elasticity, and there is a disadvantage in that a residual deformation is left because of a small interval between particles.

Accordingly, there is a continuing effort to develop a photonic crystal film that can exhibit full-color dynamic discoloration such as chameleon in a field of dyestuff changing photonic crystal film and can not leave residual deformation after dynamics change due to stress and elongation.

Accordingly, the present inventors have made efforts to develop a photonic crystal film that can exhibit full-color dynamic discoloration such as chameleon and does not leave residual strain after dyestuff change due to stress and elongation. In the course of developing a non-contact type photonic crystal Structure dynamics discoloration The photocrystalline composite, preferably a photonic crystal film, provides a large deformation to the matrix using the elasticity, leaving no residual deformation, and from this it is possible to achieve full color dynamics discoloration like a chameleon, Completed.

In addition, the photocatalytic complex of the present invention, preferably a photocatalytic composite, is a relatively simple manufacturing method which is achieved by dispersing photonic crystal particles in a polymer matrix and then irradiating the photocrystalline particles with a roll-to- roll or jet process, and it is possible to easily and continuously produce a photonic crystal composite, for example, a film or a fiber.

H. Fudouzi, T. Sawada, Proc. of SPIE 2006, 6369, 63690D.

It is an object of the present invention to provide a mechanochromic photonic crystal complex.

It is still another object of the present invention to provide a method for producing the above mechanochromic photonic crystal complex.

It is still another object of the present invention to provide a dy- namic discoloration sensor including the dy- namic color changing photocatalytic composite.

In order to achieve the above object,

The present invention relates to photonic crystal particles; And

A polymer matrix;

The photonic crystal particles are dispersed in a polymer matrix,

Wherein the two adjacent photonic crystal particles form a non-contact photonic crystal structure that is spaced apart in a noncontact state.

The present invention also provides a method for producing a polymer matrix, comprising: dispersing photonic crystal particles in a polymer matrix forming monomer to prepare a dispersion (step 1); And

And polymerizing the monomer for forming a polymer matrix in which the photonic crystal particles of the step 1 are dispersed (step 2). The present invention also provides a method for producing a mechanochromic photonic crystal composite according to claim 1.

Further, the present invention provides a dy- namic discoloration sensor comprising the mechanochromic photonic crystal complex.

The mechanochromic photonic crystal complex according to the present invention not only can exhibit a full-color reflection color in a visible light region through elastic deformation but also forms a non-contact type photonic crystal structure with a sufficient distance between photonic crystal particles Since the residual strain does not appear even after the physical deformation, the durability is excellent even in continuous use, and the constant dynamics discoloration effect can be continuously exhibited, so that the reliability of the dynamics discoloration property of the composite can be improved. Also, it is confirmed that it is sensitive to physical force applied to an area of less than or equal to μm and exhibits accurate color change, and that the precision of physical force sensing is also excellent. From this, it is confirmed that a mechanochromic composite including a non-contact photonic crystal structure Can be usefully used as an epidemiological discoloration sensor applied to fingerprint recognition and the like.

As can be seen from FIG. 1 (a), it can be confirmed that the reflection color is observed from the photonic crystal structure. When the photonic crystal structure is not satisfied as in FIG. 1 (b), the reflection color does not appear, I could.
2 is a scanning electron micrograph (SEM) photograph of a cross-section of a photonic crystal film of the present invention capable of identifying silica particles of a non-contact type array.
3 is a graph showing the reflection and transmission spectra of a photonic crystal film comprising silica particles having a volume fraction (?) Of 0.33 and a diameter of 209 nm (d).
Fig. 4 is a photograph of the photonic crystal film taken at a reflection wavelength (a) and a transmission wavelength (b) after three stages of stretching force are applied to the photonic crystal film of the present invention.
5 is an optical microphotograph of a photonic crystal film prepared from a photo-curable dispersion having diameters of silica particles of d = 148, 166, 175, 195, and 216 nm, respectively, at a volume fraction of 0.33 ) And a reflection spectrum (b) graph, and is a graph (c) showing the correlation of the reflection wavelength? Max according to the diameter of the silica particles based on the graph.
6 is an optical microscope photograph (a) of a photonic crystal film prepared from a photocurable dispersion having a volume fraction (φ) of 150 nm diameter silica particles having φ = 0.1, 0.2, 0.26, 0.33, (C) showing the dependency of the reflectance peak position on the volume fraction based on this graph (λmax (black rectangle) and full width maximum (Δλ, λmax) (red triangles) ).
7 (a) shows an optical microscope image and a CIE plot showing the structural color shifted to a short wavelength according to the elongation stress (ε) (silica particle, d (diameter) = 195 nm, φ (volume fraction) = 0.33 ). (b) shows the reflection spectrum according to various extension rates. (c) is a graph showing lambda max (black square) and Poisson ratio (red circle) according to the elongation force, (d) is a graph showing the reflection index constant (n) between two adjacent slices, And? Max, where one slice contains the (111) plane and the other slice contains the intermediate plane (silica particles, d ( Diameter portion) = 195 nm, φ (volume fraction) = 0.33, and the insets of the graphs (c) and (d) show structures corresponding to elongations 0, 21, 41.2, and 60.8%, respectively).
8 is a graph showing the reflection wavelength (λ max) measured by repeatedly applying a force corresponding to 0% to 40% elongation to the photonic crystal film of the present invention more than 20 times (silica particles, d (diameter) = 195 nm,? (volume fraction) = 0.33).
FIG. 9A is a schematic view showing the compression applied to the photonic crystal film of the present invention by a pattern stamp, FIG. 9B is a schematic view of a photomicrograph of the photonic crystal film before applying pressure to the photonic crystal film of the present invention with a small K and a large K- (C) shows the reflection spectrum at the background after the compression of the photonic crystal film (pink line, around the K stamp of the film at the lower right of (b)), and FIG. (The film at the lower left of the orange line, (b)) and the reflection spectrum of the film after compression (the light green line, the entire film area at the lower right of the film (b)), (D) and (e) are graphs showing the reflection spectra (dark green) of only the K partial area, and (d) and (e) are optical microscope images of the photomicrograph It is a photograph.
10 is a schematic view showing an embodiment of the method for manufacturing a photonic crystal film of the present invention.
Fig. 11 shows the stress-strain curve (a) and the Young's modulus (b) graph of the PEGPEA with and without silica particles.
Of Figure 12 (a) is a photonic crystal film surface of the present invention produced after photocuring SF ₆ treated and an optical micrograph taken after (Bare film) and process (reflection mode), (b) is a SF ₆ the processed film and in a SEM (scanning electron microscope) videography the surface picture, (c) is a reflection spectrum graph of the SF ₆ treatment before (red line) and post-treated (black line), (d) is a SF _6-treated film surface. (67.7 °), and (e) is a photograph of the contact angle of water droplets on the surface of the film with the elapse of 7 days after the SF ₆ treatment on the 0th day.
Figure 13 (a) shows the deformation of the fcc lattice according to the strains of ε = 0, 21, 41.2 and 60.8%, where the first image shows the fcc lattice with multiple planes embedded, the second ) And the third (blue plane) are views separated by three planes corresponding to the respective red and blue planes among the plurality of planes embedded in the plane, (b) And a slice (black color) including an intermediate plane thereof.

Hereinafter, the present invention will be described in detail.

It is to be understood, however, that the following description is provided to assist in understanding the present invention, and the present invention is not limited thereto.

The present invention relates to photonic crystal particles; And

A polymer matrix;

The photonic crystal particles are dispersed in a polymer matrix,

Wherein the two adjacent photonic crystal particles form a non-contact photonic crystal structure that is spaced apart in a noncontact state.

Here, the photonic crystal particles may be used without limitation as long as they are capable of forming a photonic crystal structure so that the photonic crystal complex exhibits a reflection color. For this purpose, it is preferable that the photonic crystal grains have a feature of including a hydrophilic group on the surface thereof have. The photonic crystal particles may also include silica particles, polystyrene particles, polymethylmethacrylate particles, polysulfone particles, melanin particles, titanium dioxide particles, iron oxide particles, aluminum oxide particles, zirconium oxide particles, and zinc oxide And particles comprising at least one selected from the group consisting of particles.

Particularly, when particles having a hydrophilic group are dispersed in the polymer matrix, gravitational layers such as a polymer matrix forming monomer and a hydrogen bond act to form a solvated layer around the particles, and the solvated layer formed on each particle has mutual repulsion Thereby making it possible to achieve the non-contact type photonic crystal structure to be achieved by the present invention.

Here, the non-contact type photonic crystal structure refers to a photonic crystal structure formed so as to have a sufficient distance between photonic crystal grains. It can be understood that this is achieved by the monomer for forming a polymer matrix used in the present invention, But is not limited to.

The size of the photonic crystal particles may be 5 to 2,000 nm, preferably 50 to 1,000 nm, more preferably 100 to 800 nm, and the size of the photonic crystal particles may be a photonic crystal that efficiently reflects visible light and near- May be greater than or equal to 100 nm and may be less than or equal to 800 nm. A more preferred range for the range of the reflection color of the photonic crystal film of the present invention from the ultraviolet region to the infrared region is 100 nm to 500 nm.

Here, the size of the photonic crystal particle can be understood to mean the longest length of the particle, and the shape of the particle is not limited to a spherical shape, but it can be understood that it is preferably a diameter (diameter).

Meanwhile, the particle size is one of the main factors for determining the reflection color represented by the dyestuff changing color photocathode composite of the present invention. In the following Examples and Experimental Examples, the correlation between the particle size and the reflection wavelength is described have. Thus, it will be appreciated by one of ordinary skill in the art that the range of particle sizes can be easily controlled in determining the color of the dyestuff changing color photocrystalline composite to be achieved by the present invention. Therefore, it should be understood that the present invention is included in the scope of the present invention if the particle size is within the range of achieving the color of reflection to be achieved by the present invention.

The photonic crystal particles are dispersed in the polymer matrix to form a photonic crystal structure, for example, an fcc structure (face-centered cubic structure), and the photonic crystal particles can exhibit a reflection color. From the viewpoint of refraction, And the refractive index difference of the polymer matrix increases, the reflection signal due to the photonic crystal increases, but the background signal also increases due to scattering by the particles. That is, when the refractive index difference between the particles and the matrix is too low to about 0.01 or less, it is transparent, but the reflection signal is weak and it is difficult to exhibit the color. When the refractive index difference is too large, about 0.05 or more, However, the values for the difference in refractive index are relative, and can be appropriately adjusted by those skilled in the art, and the present invention is not limited thereto.

The non-contact type photonic crystal structure is not particularly limited as long as the distance between the photonic crystal particles, that is, the straight line distance between the adjacent two particle surfaces can represent the reflection color to be achieved by the present invention, For example, 13% to 95% of (d ₁ + d ₂ ) / 2, when two adjacent particles among the photonic crystal particles of the present invention are selected and the longest length of each of the two particles is d ₁ and d ₂ , Refers to a non-contact photonic crystal structure spaced apart from a contactless state by a length of, for example, 15% to 100%, 18% to 95%, and 20% to 95%.

When the spacing ratio is as low as 13% or less, there is a problem in that it causes a great resistance to deformation in terms of deformation and discoloration of the film of the present invention, and may cause breakage or damage of the film due to deformation. Further, if the distance is more than 95%, it is difficult to form and maintain the photonic crystal structure, and optical characteristics may be lost or exhibited as undesirable characteristics.

Here, the longest length refers to the size of the unconstrained particles, and the shape of the particles is not limited to a spherical shape, but can be understood to be preferably a diameter (diameter). In addition to this, it is to be understood that the maximum length of the linear distance that does not penetrate or penetrate the particle three-dimensionally is the longest length, and even when the particle has an irregular shape When projected in three dimensions to indicate the length from one point on the surface of the particle to another point on the other surface, the double maximum length can be understood to be the longest length. Further, it can be understood that the length of the diameter (diameter) is preferably the longest when it is preferably spherical.

The ratio range of the distance between the particles indicates a preferable range for the individual photonic crystal particles of the dyestuff changing photocathode composite to be produced to exhibit the non-contact type photonic crystal structure. As a person skilled in the art, It is easily understood that the distance between the photonic crystal particles is within the scope of the present invention so long as a complex capable of exhibiting a reflection color and capable of restoring the same physical force to an elastic body as the elastic force can be achieved .

On the other hand, the photonic crystal particles of the present invention are preferably all spherical, but not limited to, particles of a shape, for example, a shape that is not spherical but close thereto, and all other particles that are not spherical. That is, the photonic crystal particles of the present invention can be formed into the photonic crystal particles of the present invention without limitation as long as the photonic crystal particles are formed in the photonic crystal film of the present invention so as to exhibit the desired reflection color, and the scope of the present invention will be apparent to those skilled in the art.

The photonic crystal particles of the present invention form a non-contact type photonic crystal structure as described above. The volume ratio of the photonic crystal grains retaining the non-contact type photonic crystal structure is about 50 times as large as the volume of all the photonic crystal grains contained in the film. Or more, 60% or more, 70% or more, 80% or more, 85% or more, 900% or more, 92% or more, 95% or more, 98% or more, 99% or more and 100%.

When the volume ratio of the photonic crystal particles forming the non-contact type photonic crystal structure is lowered to 50% or less, the color of the composite of the present invention does not appear, is unclear, , And other optical characteristics may be degraded or lost.

In addition, the non-contact type photonic crystal complex is obtained from inter-particle mutual repulsive force capable of inducing a sufficient separation distance between photonic crystal particles, wherein the polymer matrix, preferably a monomolecular for forming a polymer matrix, surrounds the particles, Lt; / RTI >

Specifically, the inventors of the present invention have found that a precursor of the polymer matrix, that is, a monomer (monomer) for forming a polymer matrix forms a solvated layer on the surface of a photonic crystal particle by the force of hydrogen bonding with particles, It was confirmed that an arrangement of a spontaneous non-contact photonic crystal structure can be formed from the repulsive force between particles. Thereafter, the photo-curing state was maintained while maintaining the above arrangement, and a composite was produced. From this, not only the dy- namic optical characteristics were exhibited, but also the repulsive physical force And thus a complex having excellent reversibility was produced. Thus, the present invention has been completed.

The photonic crystal particles may be 10% to 50% of the total volume of the non-contact type photonic crystal complex, although they are not particularly limited as long as they are a volume fraction that can be dispersed in the polymer matrix in the arrangement of the photonic crystal structure. 10% to 40%, 15% to 40%, 20% to 50%, and 20% to 50%.

When the volume fraction is more than 50%, the interval between the photonic crystal particles is reduced to cause a limit of the complex deformation, causing problems such as breakage of the composite. When the volume fraction is less than 10%, a distance The particles are spaced apart from each other, which makes it difficult to form and maintain the photonic crystal structure, resulting in the loss of the reflection color of the composite, the disappearance of optical characteristics, and the observation of undesired optical characteristics.

On the other hand, the polymer matrix is not particularly limited as long as it can form a solvated layer on the surface of the photonic crystal particle, but may be a polymer such as poly (ethylene glycol) phenyl ether acrylate (PEGPEA), poly (ethylene glycol) phenyl ether methacrylate, At least one polymer selected from the group consisting of phenyl ether acrylate (EGPEA), ethylene glycol phenyl ether methacrylate, alkyl acrylate, EA (ethyl acrylate) and ethylene vinyl acetate (EVA) More preferably, poly (ethylene glycol) phenyl ether acrylate (PEGPEA) can be used.

As specific examples, one or more of the following compounds may be used.

In addition, the present invention can provide the photonic crystal complex as a mechanochromic photonic crystal film. The photocatalytic composite can be easily produced by deforming the shape. Particularly, the dispersion liquid prepared as a liquid phase after the step of dispersing the photonic crystal particles in the polymer matrix can be easily changed in shape, and can be produced as a film or a fiber . In particular, those skilled in the art can understand that the present invention is not limited to the above-described shape changes, but may be modified and modified while maintaining the reflection color and dynamic color change characteristics of the photonic crystal composite.

Meanwhile, in the present invention, dyestuff discoloration characteristics were confirmed by a film having a non-contact type photonic crystal structure, and excellent dynamic dyestuff characteristics, durability, reliability, precision and sensitivity of the film were confirmed.

Accordingly, when a film or composite having a non-contact type photonic crystal structure manufactured according to the present invention is used as a dy- namic discoloration sensor, it is possible to provide excellent durability, measurement reliability, durability and product durability of a sensor, Colorimetric sensors and the like.

Specifically, the mechanochromic photonic crystal film of the present invention indicates discoloration from physical deformation of the film, for example, stretching, shrinking, pressing, etc., and the photonic crystal film of the present invention exhibits an increase in strain The blue shift indicates the color shifted to a short wavelength. At this time, in order to confirm the reuse of the photonic crystal film of the present invention with repetitive physical force, 0-40% stretching force was repeatedly applied. As a result, the reflection wavelength of the photonic crystal film of the present invention was kept constant, And it was confirmed that it still exhibited a constant reflection wavelength. Therefore, the photonic crystal film of the present invention was found to be a film exhibiting excellent durability and mechanical durability, which can be repeatedly deformed by using an elastic force, exhibits a constant reflection wavelength without any residual strain due to deformation, and exhibits durability. This reversibility is one of the great advantages achieved by the present invention. When the photonic crystal film of the present invention is used as a dyestuff dyestuff sensor in the industrial field, excellent durability is provided, repetitive and continuous use is enabled, And can provide superior product quality.

On the other hand, since the photonic crystal particles of the present invention form an array in a non-contact manner, the film has a sufficient distance between the photonic crystal particles, and the film has elasticity similar to that of an elastomer made only of a polymer matrix Since it can be understood that it is accompanied by deformation by virtue of elastic force in showing the characteristic of dynamic discoloration, complete recovery by elastic force is possible after deformation and confirmed in the following examples and experimental examples of the present invention.

Therefore, the photonic crystal complex of the present invention, preferably a film, can be continuously used, and can exhibit constant dynamics discoloration characteristics continuously. Specifically, the dy- namic color-changing photonic crystal film of the present invention is not limited thereto, but is preferably 200 MPa or less, 100 MPa or less, 50 MPa or less, 30 MPa or less, 20 MPa or less, 10 MPa or less, 8 MPa or less, , 3 MPa or less, and 1 MPa or less (elastic modulus, Young's modulus, Young modulus).

If the modulus of the composite is more than 200 MPa, the film may not be completely restored to its original shape after the film is deformed by the physical force, residual strain may remain, or the composite may be broken, It is difficult to achieve the dyestuff dyestuff complex having excellent durability that the present invention is intended to provide.

The dyestuff chromatic photonic crystal film of the present invention may have an ultimate strain of at least 10%, at least 15%, at least 20%, at least 30%, at least 50%, at least 70%, at least 80% Lt; / RTI >

If the final strain value is less than 10%, the flexibility of the composite is low, which may be inadequate to exhibit dy- namic discoloration characteristics, or the product durability may deteriorate.

According to the present invention, the dyestuff changing photocrystalline composite achieved by the present invention is obtained by selecting the photonic crystal grains and the polymer matrix capable of securing a sufficient separation distance, from the non-contacting photonic crystal structure achieved thereby, It is possible to completely recover to the initial shape based on the elastic force equal to that of the elastic body even with the applied physical force and to exhibit excellent durability and repeated dynamics discoloration characteristic even in repeated use and sufficient or broad range of deformation due to physical force, To provide a useful dyestuff colorant complex.

Therefore, all of the photonic crystal particles, the polymer matrix, and the photonic crystal complexes and the like, which can be selected within a range capable of achieving the non-contact photonic crystal structure, can be understood within the spirit of the present invention. , Which is obvious to those skilled in the art.

Further, although the photonic crystal film of the present invention is not limited to physical strain, it preferably exhibits a reflection color with a wavelength in the visible light region, a wavelength of 100 to 1000 nm and a wavelength of 200 to 800 nm, Should be understood to be included in the colorimetry to be achieved in the present invention without limitation as long as it can be achieved by deformation in the range or by adjusting the particle and volume fraction.

The range of the reflection color or the range of the reflection wavelength described above is not particularly limited and can be suitably adjusted according to the purpose of the photonic crystal complex of the present invention. For example, the range to be used as a dy- .

Further, the present invention provides a method for producing a polymer matrix, comprising: dispersing photonic crystal particles in a polymer matrix forming monomer to prepare a dispersion (step 1); And

And polymerizing the monomer for forming a polymer matrix in which the photonic crystal particles of the step 1 are dispersed (step 2). The present invention also provides a method for producing a mechanochromic photonic crystal composite.

Hereinafter, a method of manufacturing the photonic crystal composite of the present invention will be described in detail.

In the method for producing the photonic crystal complex of the present invention, the step that can be performed before step 1 may be a step of preparing the photonic crystal particles.

Here, the photonic crystal particles may be directly manufactured or used, or a commercially available product may be purchased and used immediately, or may be used after being appropriately treated. Silica particles can be used as a specific example of the photonic crystal particles, and the particles can be prepared and used as in step 1 of Example 1 of the present invention. It is preferable that the photonic crystal particles used in the present invention have a mean longest length or an average diameter, or a narrow range, but are not particularly limited.

In the method for producing a photonic crystal composite of the present invention, step 1 is a step of dispersing photonic crystal particles in a monomer for forming a polymer matrix to prepare a dispersion.

In this case, when the polymer matrix is in a liquid state at room temperature or easily heated to a liquid state, or in the case of flowing or fluid, the photonic crystal particles can be simply added and dispersed, or the polymer matrix can be dispersed by using a suitable solvent, Can be dispersed. Here, the dispersion step may be performed by adjusting the time, physical force, and the like to such an extent that the photonic crystal particles can form a photonic crystal arrangement, and the kind and amount of the solvent may be used without any particular limitation as far as the photonic crystal arrangement can be achieved .

Also, in the dispersion of step 1, a photoinitiator may be further added to prepare a dispersion. The photoinitiator is characterized in that radicals are generated by irradiation with UV light. Particularly, in the ultraviolet wavelength region of 320 nm To 380 nm, preferably from 330 nm to 375 nm, and more preferably from 340 nm to 370 nm, a radical is generated and light curing reaction is started. For example, the photoinitiator may be selected from the group consisting of anthraquinone, anthraquinone-2-sulfonic acid, sodium salt monohydrate, benzene tricarbonylchromium, benzoin ethyl ether, benzoin isobutyl ether, benzoin methyl ether, benzophenone, 4-benzoylbiphenyl, and the like. ), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (dimethylamino) benzophenone [ benzophenone, dibenzosuberenone, 2,2-dimethoxy-2-phenylacetophenone, 3,4-dimethylbenzophenone, 3'-hydroxyacetophenone, 2-hydroxy-2-methyl propiophenone, 2-hydroxy-4'- (2-hydroxy-4'- (2-hydroxyethoxy) -2-methyl propiophenone], 1-hydroxycyclohexyphenylketone, Methylbenzoyl formate, diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide, phosphine oxide phenyl bis (2,4,6-trimethylbenzoyl) 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1 (4-morpholinyl) -1-propanone}, 2-benzyl-2- (dimethylamino) -1- [4- Phenyl] -1-butanone, 2-dimethylamino-2- (4-morpholinyl) -Methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan- -phenyl) -butan-1-one], bis (5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro- 3 (1 H-pyrrol-1-yl) -phenyl) titanium [bis (.eta.5-2,4-cyclopentadien- 1- yl) -bis (2,6- difluoro-3- phenyl-titanium, 2-isopropyl thioxanthone, 2-ethylanthraquinone, 2,4-diethyl thioxanthone, benzyl Benzyl benzoate, benzyl benzoate, benzyl benzoate, benzyl benzoate, benzyl benzoate, benzyl benzoate, benzyl benzoate, benzyl benzoate, benzyl benzoate, ), 2,2'-bis (2-chlorophenyl) -4,4'-5,5'-tetraphenyl-1,2'- 4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole], 2,2', 4-tris (2- chlorophenyl) -5- (3,4-dimethoxyphenyl) -4- Diphenyl-1,1'-biimidazole [2,2 ', 4-tris (2-chlorophenyl) -5- (3,4-dimethoxyphenyl) -4', 5'- , 1'-biimidazole], 4-phenoxy-2 ', 2'-dichloro acetophenone and ethyl 4- (dimethylamino) benzoate [ethyl-4 - (d (dimethylamino) benzoate], 2-ethylhexyl-4- (dimethylamino) benzoate, isoamyl 4- (dimethylamino) benzoate, , 4,4'-bis (diethylamino) benzophenone], 4- (4'-methylphenylthio) - benzophenone [ benzophenone], 1,7-bis (9-acridinyl) heptane, n-phenyl glycine, and 2-hydroxy-2- methyl And 2-hydroxy-2-methylpropiophenone. Among them, anthraquinone-2-sulfonic acid (sodium salt monohydrate), benzoin ethylether, benzoin isobutyl ether (hereinafter referred to as " benzoin isobutyl ether, benzoin methyl ether, dibenzosuberenone, 2,2-dimethoxy-2-phenylacetophenone, 3,4 3,4-dimethylbenzophenone, 3'-hydroxyacetophenone, 2-hydroxy-2-methyl propiophenone and the like are preferable and,

More preferably, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-1- [4- (2-hydroxyethoxy) Methyl-1- [4- (methylthio) phenyl] -2-morpholin-2- (2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,2-dimethoxy-2-phenylacetophonone and 2-benzyl-2-dimethylamino- (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1) and 1-hydroxycyclohexyl phenyl ketone At least one selected from the group consisting of

The photoinitiator may be used in view of allowing sufficient photo-curing reaction to proceed when irradiated with ultraviolet (UV) light. However, when the photoinitiator is used in an excessive amount, there may arise a problem of absorbing light in the visible light region to inhibit the transmittance of the photonic crystal complex.

On the other hand, in order to effectively achieve the dispersion of the step 1, additional additives may be used and further additives conventionally known, for example, a dispersant may be further dispersed.

In the method for producing a photonic crystal composite of the present invention, Step 2 is a step of polymerizing the polymer matrix-forming monomer in which the photonic crystal particles of Step 1 are dispersed.

Step 2 is a step of polymerizing the polymer matrix in which the photonic crystal particles of the dispersion prepared in Step 1 are dispersed, for example, thermal curing, thermal polymerization, photo-curing or photopolymerization.

In this case, the photocuring or photopolymerization refers to a polymerization or curing of a component constituting the polymer matrix by irradiating light, for example, photopolymerization or photo-curing starting from a photoinitiator. The polymer matrix can be used without limitation as long as it can be cured. For example, the wavelength range of light to be irradiated, such as UV irradiation, can be used for light irradiation in a wavelength range used in conventional photopolymerization or photocuring methods.

As described above, the method of producing the photonic crystal composite of the present invention can be carried out by simply dispersing silica particles in a selected polymer matrix, thereby forming a non-contact type photonic crystal structure with repulsive force by the solvated layer, Which is applicable to roll-to-roll or jet processes and has the advantage that it can be continuously produced as a dyestuff changing film or fiber for general purpose use.

Meanwhile, the manufacturing method of the photonic crystal composite of the present invention may further include a step of post-treating the film produced after the step 2.

For example, after the polymerization of step 2, the step of treating the surface of the composite thus prepared may further include (step 4). Here, the surface treatment step may be understood as a method for solving the inconvenience of handling the film later due to low surface energy of the composite produced after step 2, for example, film. For example, the etching process can be performed. In the specific embodiment of the present invention, surface energy was increased by treating with SF ₆ -, and it was confirmed that a sharp dynamics discoloration characteristic still appeared after the treatment.

Further, the present invention provides a mechanical dyesensor including the mechanochromic photonic crystal film.

Here, the dy- namic discoloration sensor can represent the physical force applied to the sensor as a change in color, and it is possible to analyze the physical force applied thereto, or analyze the pattern in the direction of the applied force from the difference in color for each area can do. Examples of the application include a fingerprint recognition sensor, a colorimetric sensor, and the like.

At this time, the dy- namic color change sensor including the mechanochromic photonic crystal composite of the present invention can be easily deformed in its original form due to elasticity even after deformation due to a force applied from a non-contact type structure in which the distance between photonic crystal particles is sufficiently spaced Can return, can extend the range of the maximum force applied, and exhibits features that can be repeatedly used without residual deformation. Therefore, the dyestuff color sensor of the present invention exhibits excellent durability and can significantly improve the quality of a product using the same.

In order to analyze the characteristics of the photocatalytic composite of the present invention, it was made into a film and subjected to experiments such as dyestuff fading characteristics, sectional photographing, Young's modulus measurement, SF ₆ treatment,

First, in the optical observation of the present invention, the photonic crystal film of the present invention was able to observe the reflection color of the wavelength band formed by the photonic crystal structure, that is, the photonic crystal structure of the non-contact type array of photonic crystal particles .

As a result of examining the reflection and transmission spectra of the films at 0.33 volume fraction (φ) and 209 nm diameter (d) of the photonic crystal particles for the photonic crystal film, the color shift to short wavelength In other experiments, the volume fraction of silica (φ = 0.33), the diameters of the silica particles were d = 148, 166, 175, 195, and 216 nm, the correlation of the reflection wavelength? Max according to the diameter of the silica particles could be confirmed. Conversely, optical microscope photographs and reflection spectra of the films were confirmed with silica particles having diameters of 150 nm as φ = 0.1, 0.2, 0.26, 0.33, and 0.4, respectively, and the volume of reflectance peak position The fractional dependence was confirmed.

Above all, from the experiment of repeatedly applying a force corresponding to 0% to 40% elongation to the photonic crystal film of the present invention more than 20 times and observing the change of the reflected wavelength (? Max) And the excellent reversibility of the film was confirmed. From this, it was confirmed that the film of the present invention can be used as a dy- namic discoloration sensor exhibiting excellent durability even in repeated use.

The foregoing description is only for the understanding of the present invention, and the present invention is not limited thereto. In particular, it is an object of the present invention to provide a non-contact type photonic crystal structure capable of forming a non-contact type photonic crystal structure in that it is a non-contact type photonic crystal structure and a dyestuff changing color composite produced therefrom, That is, a photonic crystal particle, a polymer matrix, a polymer matrix, a polymer matrix precursor, or a polymer matrix, which are positioned around the particle, and which can generate mutual repulsive forces from each other to naturally or spontaneously form a non-contact photonic crystal structure The produced photonic crystal complex and its production method are consistent with the present invention and should be understood to be included in the present invention.

Hereinafter, the present invention will be described in detail with reference to Examples and Experimental Examples, but the present invention is not limited thereto.

< Example  1 > Preparation of non-contact photonic crystal dispersion composition 1

Step 1: Preparation of silica particles

The monodispersed silica particles were first prepared by seeding the seed particles by the two-phase method, and then growing the silica particles with d = 209 nm as the target diameter by the Stober method. Thereafter, the suspension was washed with ethanol, completely dried in a convection oven at 70 캜 for 12 hours, and the weight of the silica powder was measured.

Step 2: Preparation of dispersion

The silica powder prepared in the above step 1 was dispersed in ethanol, which was then dispersed in a solution containing a photoinitiator of 1 w / w% 2-hydroxy-2-methyl-1-phenyl-1-propanone (Darocur 1173, Ciba Chemical) PEGPEA (Mw 324, Sigma-Aldrich). At this time, the amount of PEGPEA was determined to be the weight of the silica powder so that the objective volume fraction of ethanol-free silica particles of? = 0.33 was achieved. The density of the silica particles and PEGPEA was about 2.0 and 1.127 g / mL, respectively. The mixed solution prepared in the above procedure was completely dried in a convection oven at 70 DEG C for 12 hours to remove ethanol to obtain the desired photo- Non-contact photonic crystal dispersion composition).

< Example  2 > Preparation of non-contact photonic crystal dispersion composition 2

The procedure of Example 1 was repeated, except that the diameter of the objective silica particles was set to d = 148 nm and the objective volume fraction of the silica particles was set to be 0.33. Thus, a desired non-contact type photonic crystal dispersion composition .

< Example  3> Preparation of non-contact photonic crystal dispersion composition 3

The procedure of Example 1 was repeated, except that the diameter of the objective silica particles was set to d = 166 nm and the objective volume fraction of the silica particles was set to be 0.33, so that the desired non-contact type photonic crystal dispersion composition .

< Example  4> Preparation of non-contact photonic crystal dispersion composition 4

The procedure of Example 1 was repeated, except that the diameter of the target silica particles was set to d = 175 nm and the target volume fraction of the silica particles was set to be 0.33, to obtain the desired non-contact type photonic crystal dispersion composition .

< Example  5> Preparation of non-contact photonic crystal dispersion composition 5

The procedure of Example 1 was repeated, except that the diameter of the objective silica particles was set to d = 195 nm and the objective volume fraction of the silica particles was set to be 0.33, so that the desired non-contact type photonic crystal dispersion composition .

< Example  6> Preparation of non-contact photonic crystal dispersion composition 6

The procedure of Example 1 was repeated, except that the diameter of the target silica particles was set to d = 216 nm and the target volume fraction of the silica particles was set to? = 0.33 to obtain the desired non-contact type photonic crystal dispersion composition .

< Example  7> Preparation of non-contact photonic crystal dispersion composition 7

The procedure of Example 1 was repeated, except that the diameter of the target silica particles was set to d = 150 nm and the target volume fraction of the silica particles was set to? = 0.1, to obtain the desired non-contact type photonic crystal dispersion composition .

< Example  8> Preparation of non-contact photonic crystal dispersion composition 8

The procedure of Example 1 was repeated, except that the diameter of the target silica particles was set to d = 150 nm and the target volume fraction of the silica particles was set to? = 0.2 to obtain the desired non-contact type photonic crystal dispersion composition .

< Example  9> Preparation of non-contact photonic crystal dispersion composition 9

The procedure of Example 1 was repeated, except that the diameter of the target silica particles was set to d = 150 nm and the target volume fraction of the silica particles was set to? = 0.26, to obtain the desired non-contact type photonic crystal dispersion composition .

< Example  10> Preparation of non-contact photonic crystal dispersion composition 10

The procedure of Example 1 was repeated, except that the diameter of the target silica particles was set to d = 150 nm and the target volume fraction of the silica particles was set to? = 0.33 to obtain the desired non-contact type photonic crystal dispersion composition .

< Example  11> Preparation of non-contact photonic crystal dispersion composition 7

The procedure of Example 1 was repeated, except that the diameter of the target silica particles was set to d = 150 nm and the target volume fraction of the silica particles was set to? = 0.4 to obtain the desired non-contact type photonic crystal dispersion composition .

The non-contact photocrystalline dispersion compositions prepared in Examples 1 to 11 are shown in Table 1 below.

Example Diameter of silica particles (d, nm) Volume fraction (?,%) Of silica powder One 209 0.33 2 148 0.33 3 166 0.33 4 175 0.33 5 195 0.33 6 216 0.33 7 150 0.1 8 150 0.2 9 150 0.26 10 150 0.33 11 150 0.4

< Experimental Example  1> dynamics discoloration 기계초 ) Photonic crystal  Production of film 1

In order to produce the dyestuff photographic crystal film according to the present invention, the following procedure was carried out.

The production of the photonic crystal film of the present invention can be understood from the schematic diagram shown in FIG. 10, and specifically, can be made by performing the following step 1.

Step 1: Photonic crystal  Production of film

The non-contacting photocrystalline dispersion composition prepared in Examples 1-11, that is, the photocurable dispersion, was infiltrated into a 50 μm thick space between two polyimide tapes (Kapton) with spontaneous capillary force. Then, the infiltrated dispersion was irradiated with UV light (innocent 100N, Lichtzen) at an intensity of 2 W / cm ² for 20 seconds to photo-cure. Only the photocured composition film produced therefrom was peeled off to produce a desired photonic crystal film.

< Experimental Example  2> Mechanics of discoloration ( 기계초 ) Photonic crystal  Production of film 2

The following experiment was conducted to further evaluate the properties of the photocatalytic film according to the present invention.

First, the surface treatment step was performed in step 1 of Experimental Example 1, and then the film surface treatment step in Step 2 was further performed to prepare a surface-treated photonic crystal film.

Step 2: Surface treatment of film

To lower the surface energy of the film, both surfaces of the film were treated by reactive ion etching (VSRIE-400A, Vaccum Science inc.) At a flow rate of 100 sccm at 150 W power, SF ₆ (sulfur hexafluoride) for 30 seconds, Finally, a desired surface-treated photonic crystal film was prepared.

The following experiment was conducted to compare the photonic crystal film before surface treatment prepared in Experimental Example 1 and the surface treated photonic crystal film prepared in Experimental Example 2 with each other. Specifically, an optical microscope and a scanning electron microscope (SEM) photograph of the surface of the film were taken, the reflection spectrum was measured, the contact angle with respect to the water droplet was measured on the surface of the film, and the surface energy was measured. .

Of Figure 12 (a) is a photonic crystal film surface of the present invention produced after photocuring SF ₆ treated and an optical micrograph taken after (Bare film) and process (reflection mode), (b) is a SF ₆ the processed film and in a SEM (scanning electron microscope) videography the surface picture, (c) is a reflection spectrum graph of the SF ₆ treatment before (red line) and post-treated (black line), (d) is a SF _6-treated film surface. (67.7 °), and (e) is a photograph of the contact angle of water droplets on the surface of the film with the elapse of 7 days after the SF ₆ treatment on the 0th day.

Contact angle with water droplet Experimental Example 1
(Non-surface treated photonic crystal film) 67.7 [deg.] Experimental Example 2
(0 days after SF ₆ treatment) 137.7 [deg.] Experimental Example 2
(1 day after SF ₆ treatment) 127.6 [deg.] Experimental Example 2
(7 days after SF ₆ treatment) 104.9 DEG

Referring to Figure 12, As will be identified in (a) SF ₆ the film surface after the treatment can be confirmed that becomes more vivid, (b) a SEM in SF ₆ a foreign substance on the surface are removed after the treatment to observe a clear film surface have. In addition, (c) the reflection spectrum graph shows that the desired optical characteristics (reflection color) still appear before and after the treatment. Particularly, (d) the contact angle with the water droplet shows that the water droplet is 67.7 And the surface energy of the film is low due to the fact that the water droplet is spread widely. On the other hand, it was confirmed from the contact angle of 137.7 ° at the 0th day after the surface treatment that the SF ₆ surface treatment effect was excellent. On the other hand, the surface treatment effect was somewhat decreased with 1 day and 7 days, It can be confirmed that a considerably excellent contact angle (1 day = 127.6 °, 7 days = 104.9 °) is maintained.

Therefore, the photonic crystal film of the present invention can further include a surface treatment step, from which it can exhibit still excellent coloring characteristics, can lower the surface energy of the produced film, It is possible to provide convenience.

< Experimental Example  3> Photonic  Check 1

The following experiment was conducted to confirm the photocrystallinity of the dyestuff chromatic photonic crystal film of the present invention.

Specifically, in order to confirm whether a desired photonic crystal structure was formed on the photonic crystal film prepared in Experimental Example 1, a film was placed on a printed matter having a typeface, and whether or not a reflection color appeared And the formation of a photonic crystal structure was confirmed. The results are shown in Fig.

As can be seen from FIG. 1 (a), it can be confirmed that the reflection color is observed from the photonic crystal structure. When the photonic crystal structure is not satisfied as in FIG. 1 (b), the reflection color does not appear, I could.

As can be seen from FIG. 1 (a), it can be confirmed that the reflection color is observed from the photonic crystal structure. When the photonic crystal structure is not satisfied, light is not reflected, And it was confirmed that the light was transmitted.

Therefore, it was confirmed that the photonic crystal film of the present invention can exhibit a reflection color.

< Experimental Example  4> Photonic  OK 2

The following experiment was conducted to confirm the photocrystallinity of the dyestuff chromatic photonic crystal film of the present invention.

Specifically, in order to confirm whether the non-contact type photonic crystal dispersion composition of the present invention was formed on the photonic crystal film prepared in Experimental Example 1, the cross section of the film was photographed with a scanning electron microscope (SEM) Is shown in Fig.

2 is a scanning electron micrograph (SEM) photograph of a cross-section of a photonic crystal film of the present invention capable of identifying silica particles of a non-contact type array.

Referring to FIG. 2, it can be seen from the SEM image that the photonic crystal film of the present invention has sufficiently separated silica particles and has an array of photonic crystal structures. As a result, it can be seen that the non- .

Thus, it can be clearly seen that the photonic crystal film of the present invention is a structure in which a non-contact type photonic crystal dispersion composition is formed.

< Experimental Example  5> Photonic crystal  Reflection and transmission spectra of film

The following experiment was conducted to confirm the reflection color of the dyestuff chromatic photonic crystal film of the present invention.

Specifically, the reflection and transmission spectra of the photonic crystal films prepared from the non-contact photocrystalline dispersion composition (0.33 (?), 209 nm (d)) of Example 1 were measured and the results are shown in FIG.

3 is a graph showing the reflection and transmission spectra of a photonic crystal film comprising silica particles having a volume fraction (?) Of 0.33 and a diameter of 209 nm (d).

As can be seen from Fig. 3, the reflected spectrum (black line) amplified at the wavelength band of about 670 to 680 nm can be confirmed, and it can be confirmed that the reflection color appears, and the reduced transmission spectrum Ray of the wavelength range of 670 to 680 nm is reflected from the film.

< Experimental Example  6> Evaluation of mechanical dyes

The following experiment was conducted to confirm the dynamic discoloration characteristics of the dyestuff chromatic photonic crystal film of the present invention.

Specifically, in order to confirm the dynamic discoloration characteristics of the photonic crystal film produced from the non-contact type photonic crystal dispersion composition (0.33 (φ), 209 nm (d)) of Example 1, a stretching force was applied in three steps A strong force was gradually applied from the stretching force of 0). The reflection color and the transmission color appearing from the film were confirmed, and the results are shown in FIG.

Drawing force Reflection color Transmission color Stage 1 Red color Blue
(The light of the wavelength band excluding the reflection color is transmitted) Step 2 green Red color
(The light of the wavelength band excluding the reflection color is transmitted) Step 3 Blue Yellow
(The light of the wavelength band excluding the reflection color is transmitted)

Fig. 4 is a photograph of the photonic crystal film taken at a reflection wavelength (a) and a transmission wavelength (b) after three stages of stretching force are applied to the photonic crystal film of the present invention.

As can be seen from FIG. 4, when the reflection color of the left photograph with the stretching force of 0 is seen, the light of a relatively long wavelength of red is reflected, and the transmission color is the light of the wavelength excluding the reflection color have. On the other hand, when the gradually applied stretching force is increased, it can be confirmed that the reflection color gradually reflects the short wavelength light in the order of green, then blue, and in contrast, the transmission color transmits light except short- can confirm.

Therefore, the photonic crystal film of the present invention exhibits a pronounced dynamical discoloration characteristic with respect to the physical force to be applied, and it can be confirmed that the photonic crystal film gradually reflects light of short wavelength as the applied stretching force is increased.

< Experimental Example  7> Photonic crystal particles In diameter  Following Photonic crystal  Characterization of film

The following experiment was performed to observe the change of the characteristics of the dyestuffic photocrystalline photonic crystal film according to the diameter of the photonic crystal particle of the present invention.

Specifically, from the photonic crystal film having the non-contact type photonic crystal dispersion composition in which the only particle diameters of the same volume fraction (? = 0.33) of Examples 2-6 were changed to d = 148, 166, 175, 195 and 216 nm The optical microscope photographs and the reflection spectra were measured according to the change of the particle diameter, and the correlation between the particle diameter and the reflection wavelength was determined. The result is shown in FIG.

Used in photonic crystal films
Non-contact photonic crystal dispersion composition
(same with φ = 0.33) Particle diameter
(d, nm) Reflected waveband Example 2 148 470 nm Example 3 166 530 nm Example 4 175 560 nm Example 5 195 620 nm Example 6 216 690 nm

5 is an optical microphotograph of a photonic crystal film prepared from a photo-curable dispersion having diameters of silica particles of d = 148, 166, 175, 195, and 216 nm, respectively, at a volume fraction of 0.33 ) And a reflection spectrum (b) graph, and is a graph (c) showing the correlation of the reflection wavelength? Max according to the diameter of the silica particles based on the graph.

As can be seen from FIG. 5, it was confirmed that the photonic crystal film of the present invention is shifted from a short wavelength to a long wavelength by a reflected wavelength as the size of the silica particles as photonic crystal particles increases. Specifically, the array of Example 2, that is, the photonic crystal film of the silica particles having a diameter of d = 148 nm, reflects a wavelength of about 470 nm, and the array of Example 6, that is, silica particles having a diameter of d = 216 nm Of the photonic crystal film reflects a long wavelength of about 690 nm. Based on this, it can be confirmed that the relationship of the reflection wavelengths according to the particle diameters linearly increases as shown in the graph showing the correlation of the reflection wavelength? Max according to the diameter of the silica particles.

On the other hand, the black line shown in the graph (c) shows the Bragg equation for the (111) plane of the face-centered cubic structure (fcc), and the tendency of the photonic crystal film of the present invention corresponds thereto, It can be seen that the photonic crystal structure of the second embodiment is a face-centered cubic structure.

< Experimental Example  8> photonic crystal particles In volume fraction  Following Photonic crystal  Characterization of film

The following experiment was carried out to observe the change of the characteristics of the dyestuffic photovoltaic photonic crystal film according to the volume fraction of the photonic crystal particles of the present invention.

Specifically, the same particle diameters d = 150 in Examples 7-11, but with a volume fraction (φ) for only the entire photonic crystal dispersion composition of φ = 0.1, 0.2, 0.26, 0.33, and 0.4 The photomicrographs and the reflection spectra of the photonic crystal films were measured according to the volume fraction change, and the correlation between the particle volume fraction and the reflection wavelength was shown in FIG.

Used in photonic crystal films
Non-contact photonic crystal dispersion composition
(d equals 150 nm) Volume fraction
(φ) Reflected waveband Example 7 0.1 Not measured
(Photonic crystal structure is not formed) Example 8 0.2 550 nm Example 9 0.26 510 nm Example 10 0.33 470 nm Example 11 0.4 450 nm

6 is an optical microscope photograph (a) of a photonic crystal film prepared from a photocurable dispersion having a volume fraction (φ) of 150 nm diameter silica particles having φ = 0.1, 0.2, 0.26, 0.33, (C) showing the dependency of the reflectance peak position on the volume fraction based on this graph (λmax (black rectangle) and full width maximum (Δλ, λmax) (red triangles) ).

As can be seen from FIG. 6, it was confirmed that the photonic crystal film of the present invention is shifted from long wavelength to short wavelength as the volume fraction of the silica particles as the photonic crystal particles thereof increases. Specifically, in the array of Example 7, that is, the photonic crystal film having a volume fraction of? = 0.1, the volume fraction of the photonic crystal grains in the entire film is remarkably low, and the photonic crystal structure is not formed therefrom can confirm. Thus, it can be seen that no reflected wave field at? = 0.1 is observed at all. On the other hand, if the volume fraction is gradually increased, it can be confirmed that the array of Example 11, that is, the photonic crystal film having a volume fraction of? = 0.4 reflects a short wavelength of about 450 nm. Based on this, it can be confirmed that the relationship of the reflection wavelengths according to the volume fraction linearly decreases as shown in the graph showing the correlation of the reflection wavelength? Max according to the volume fraction (black square).

On the other hand, the black line shown in the graph (c) shows the Bragg equation for the (111) plane of the face-centered cubic structure (fcc), and the tendency of the photonic crystal film of the present invention corresponds thereto, It can be seen that the photonic crystal structure of the second embodiment is a face-centered cubic structure.

< Experimental Example  9> Stretching  Evaluation of mechanical dyes according to stress

The following experiment was carried out to observe the change of the characteristics of the dyestuffic photovoltaic photonic crystal film according to the volume fraction of the photonic crystal particles of the present invention.

Specifically, the stretching stress (?) Was gradually applied (? = 0%, 7.67%, 13.87%, 21%, and 10%) from the photonic crystal film having the photonic crystal dispersion composition (d = 195, (Optical microscope photographs and CIE plots and reflection spectra) were measured, and the results are shown in FIG. 7, and the results are shown in FIG. 7. The results are shown in FIGS. 7A to 7C, .

Elongation stress (?,%) Reflected waveband 0 625 nm 7.67 605 nm 13.87 590 nm 21 570 nm 27.73 555 nm 34.27 540 nm 41.2 530 nm 46.6 520 nm 53.67 510 nm 60.8 503 nm 68.67 490 nm

7 (a) shows an optical microscope image and a CIE plot showing the structural color shifted to a short wavelength according to the elongation stress (ε) (silica particle, d (diameter) = 195 nm, φ (volume fraction) = 0.33 ). (b) shows the reflection spectrum according to various extension rates. (c) is a graph showing lambda max (black square) and Poisson ratio (red circle) according to the stretching force, and (d) is a graph showing the reflection index constant (n) between two adjacent slices, And? Max, where one slice contains the (111) plane and the other slice contains the intermediate plane (silica particles, d ( Diameter portion) = 195 nm, φ (volume fraction) = 0.33, and the insets of the graphs (c) and (d) show structures corresponding to elongations 0, 21, 41.2, and 60.8%, respectively).

As shown in FIG. 7, it can be confirmed that the reflection color of the film, which is gradually increased as the stretching force applied to the photonic crystal film of the present invention increases, is gradually shifted to a shorter wavelength. As can be seen from the graphs (c) and (d), the reflected wavelength, the reflection index constant, and the Poisson's ratio can be confirmed to be decreased with the same tendency as the elongation force is increased. The photonic crystal film of the present invention has elasticity It is possible to confirm that the full dynamic color change of the complete dy- namic color change is exhibited.

Therefore, it can be seen that the photonic crystal film of the present invention exhibits a reflection color shifted to a shorter wavelength as the stretching force applied based on the elastic force is increased.

< Experimental Example  10> Photonic crystal  Evaluation of film durability

The following experiment was conducted to evaluate the durability of the dyestuff photocorrosion photocatalyst film according to the present invention, that is, dyestuff discoloration characteristics even after continuous use.

Specifically, a photocatalytic film having a photonic crystal dispersion composition (d = 195,? = 0.33) of Example 5 was applied with stretching force ε = 0% to 40%, repeatedly performed 20 times or more, The reflected wavelength from this is measured and is shown in Fig.

And
Elongation stress (?,%) Reflected waveband
([lambda] max, nm) 1 time 0 587 40 487 Episode 2 0 581 40 488 3rd time 0 582 40 486 4 times 0 580 40 486 5 times 0 581 40 488 6 times 0 582 40 488 7 times 0 581 40 487 8 times 0 581 40 488 9 times 0 581 40 487 10 times 0 581 40 487 11 times 0 580 40 486 12 times 0 581 40 485 13 times 0 585 40 486 14 times 0 582 40 485 15 times 0 584 40 484 16 times 0 581 40 483 17 times 0 583 40 484 18 times 0 583 40 485 19 times 0 583 40 483 20 times 0 583 40 482

8 is a graph showing the reflection wavelength (λ max) measured by repeatedly applying a force corresponding to 0% to 40% elongation to the photonic crystal film of the present invention more than 20 times (silica particles, d (diameter) = 195 nm,? (volume fraction) = 0.33).

As shown in FIG. 8, the photonic crystal film of the present invention exhibits a constant reflection wavelength even at a repeated stretching force, and still exhibits a constant reflection wavelength at 0% and 40%, respectively, even when a repeated stretching force of 20 times or more is applied. It can exhibit excellent mechanical durability even when repeated physical force is applied, and it shows excellent durability and shows a certain reflection wavelength even in repeated use, thus showing a remarkable characteristic that can measure precise mechanical durability You can see.

Therefore, the dyestuff chromatic photonic crystal film of the present invention can be easily restored to its original state by the elasticity of the film even with repetitive physical force, and the value of the dyestuff discoloration property is constantly maintained, which is confirmed to have excellent reliability. Accordingly, the photonic crystal film of the present invention can be used as a dynamic dyesensitization sensor, and can be effectively used as a product having excellent durability and reliability from the characteristics of the film described above.

< Experimental Example  11> Photonic crystal  Evaluation of mechanical dyes according to precision pressure of film

The following experiment was carried out to evaluate the dyestuff fading characteristics according to the precision pressing of the photonic crystal film according to the present invention.

Specifically, a relatively large (mm-sized) K-shaped stamp including a small K-shape with a minute size (μm size) was produced and pressed onto the photonic crystal film of the present invention. Observation was made with an optical microscope and naked eyes, and the results are shown in Fig.

FIG. 9A is a schematic view showing the compression applied to the photonic crystal film of the present invention by a pattern stamp, FIG. 9B is a schematic view of a photomicrograph of the photonic crystal film before applying pressure to the photonic crystal film of the present invention with a small K and a large K- (C) shows the reflection spectrum at the background after the compression of the photonic crystal film (pink line, around the K stamp of the film at the lower right of (b)), and FIG. (The film at the lower left of the orange line, (b)) and the reflection spectrum of the film after compression (the light green line, the entire film area at the lower right of the film (b)), (D) and (e) are graphs showing the reflection spectra (dark green) of only the K partial area, and (d) and (e) are optical microscope images of the photomicrograph It is a photograph.

As shown in FIG. 9, it was confirmed that the photonic crystal film of the present invention still exhibits excellent dy- namic discoloration characteristics even under pressure of a stamp produced in a unit of fine μm or less. It was also found that stamps fabricated in units of submicron μm were still closely adjacent to each other and still exhibited a clear color change depending on the stamp shape. Furthermore, it has been confirmed that the shape of the stamp can still exhibit a sharp and precise color change without limitation.

Therefore, the photonic crystal film of the present invention can express precisely and precisely the color change corresponding to the physical force applied in units of μm or less and nm or less, and exhibits excellent precision and sensitivity when used as a dynamic dyestuff sensor including the same And can be usefully used as an excellent dynamic dyes sensor.

< Experimental Example 12> Photonic crystal  Evaluation of Elasticity of Film

In order to evaluate the elasticity of the photonic crystal film having the non-contact type photonic crystal dispersion composition according to the present invention, the following experiment was conducted.

Specifically, a film made of a polymer matrix (PEGPEA) without silica particles and a silica particle was fabricated in the same manner as the photonic crystal film of the present invention. Stress-strain correlation and Young's Modulus were then evaluated for each film, and the results are shown in FIG.

Fig. 11 shows the stress-strain curve (a) and the Young's modulus (b) graph of the PEGPEA with and without silica particles.

11, the photonic crystal film according to the present invention exhibits a Young's Modulus value almost similar to that of a polymer-only film, even though silica particles are included, confirming that the photonic crystal film of the present invention is an excellent elastic body It is. In addition, as can be seen from the stress-strain curve, the photonic crystal film of the present invention shows a tendency similar to that of a polymer film only, and it can be confirmed that the film can be maintained in its elasticity even at a strain of up to 0.75 have.

Therefore, even if the photonic crystal film of the present invention contains photonic crystal particles, it has a non-contact type photonic crystal dispersion composition, so that the elastic properties of the film are close to a complete elastic body and can be fully recovered from the physical force applied thereto, From this, it can be seen that the dy- namic discoloration characteristics are shown as constant characteristic values even in continuous use, and that they have excellent reliability. Thus, the dyestuff color sensor including the photonic crystal film of the present invention can exhibit excellent durability, precision, and reliability, and is useful in all industries in which the dyestuff color sensor can be used.

Claims (19)

Photonic crystal particles; And
A polymer matrix;
The photonic crystal particles are dispersed in a polymer matrix,
Wherein the two adjacent photonic crystal particles form a non-contact photonic crystal structure that is spaced apart in a noncontact manner.
The method according to claim 1,
Wherein the non-contact type photonic crystal structure is formed in a noncontact state in a range of 13-95% of (d ₁ + d ₂ ) / 2 when the lengths of the two adjacent photonic crystal particles are d ₁ and d ₂ , Wherein the photonic crystal structure is a non-contact photonic crystal structure spaced apart from the photonic crystal structure.
The method according to claim 1,
Wherein the photonic crystal complex has a Young's modulus of 200 MPa or less.
The method according to claim 1,
The non-contact-type photonic crystal structure of the _{(d 1 + d 2) /} 2 from the mutual repulsion of the solvated layer for surrounding a respective photonic crystal particles forming the solvated layer, for the polymer matrix is placed around the optical crystal particle 13 Wherein the photonic crystal structure is a non-contact type photonic crystal structure spatially separated from the photonic crystal structure by a distance in a range of about 100 to 95%.
The method according to claim 1,
Wherein the photonic crystal complex has an Ultimate strain of 10% or more. &Lt; RTI ID = 0.0 &gt; 8. &lt; / RTI &gt;
The method according to claim 1,
Wherein the photonic crystal particles have a longest length of 100 nm to 500 nm.
The method according to claim 1,
Wherein the photocatalytic composite exhibits a reflection color with a wavelength of 200 to 800 nm according to physical deformation.
The method according to claim 1,
Wherein in the photonic crystal composite, the photonic crystal particles forming the non-contact photonic crystal structure are at least 50 wt% or more based on the weight of the total photonic crystal grains contained in the composite.
The method according to claim 1,
The polymer matrix may be selected from the group consisting of poly (ethylene glycol) phenyl ether acrylate (PEGPEA), poly (ethylene glycol) phenyl ether methacrylate, ethylene glycol phenyl ether acrylate (EGPEA), ethylene glycol phenyl ether methacrylate, , EA (ethyl acrylate), and ethylene vinyl acetate (EVA). 2. The mechanochromic photonic crystal composite according to claim 1, wherein the polymer matrix is a polymer matrix.
The method according to claim 1,
Wherein the photonic crystal particles are included in a volume ratio of 10% to 50% by volume of the total photonic crystal complex.
The method according to claim 1,
Wherein the photonic crystal particles include at least one selected from the group consisting of silica particles, polystyrene particles, polymethylmethacrylate particles, polysulfone particles, melanin particles, and iron oxide particles. Complex.
The method according to claim 1,
Wherein the photonic crystal complex is a dynamically discolored photonic crystal film formed into a film.
Dispersing the photonic crystal particles in a polymer matrix forming monomer to prepare a dispersion (step 1); And
And polymerizing the monomer for forming a polymer matrix in which the photonic crystal particles of step 1 are dispersed (step 2). &Lt; Desc / Clms Page number 19 &gt;
14. The method of claim 13,
Further comprising a step (step 3) of performing a surface treatment for increasing the surface energy of the prepared composite after the polymerization of the step 2 (step 3).
14. The method of claim 13,
Wherein the polymer matrix forming monomer is a liquid.
14. The method of claim 13,
The polymer matrix forming monomer may be selected from the group consisting of poly (ethylene glycol) phenyl ether acrylate (PEGPEA), poly (ethylene glycol) phenyl ether methacrylate, ethylene glycol phenyl ether acrylate (EGPEA), ethylene glycol phenyl ether methacrylate Wherein the monomer is a polymer matrix-forming monomer comprising at least one member selected from the group consisting of acrylate, EA (ethyl acrylate) and ethylene vinyl acetate (EVA).
14. The method of claim 13,
Wherein the dispersion of step 1 further comprises a photoinitiator. &Lt; RTI ID = 0.0 &gt; 8. &lt; / RTI &gt;
14. The method of claim 13,
The photoinitiator may be selected from the group consisting of 2-hydroxy-2-methylpropiophenone, 2-hydroxy-1- [4- (2- hydroxyethoxy) phenyl] (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,2-dimethoxy-2-phenylacetophenone , And 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 1-hydroxycyclohexyl phenyl ketone. ) Method for manufacturing a photonic crystal complex.
A dyestuff fading sensor comprising the mechanochromic photonic crystal complex of claim 1.

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