Metallic glossy material

Abstract

To provide a novel metallic luster material using an organic dye containing no metallic element, a method for producing the material, and a novel method for using the organic dye containing no metallic element that produces metallic luster.SOLUTION: A metallic luster material in which organic dyes containing no metallic elements are supported on a support, is stretched in at least one direction and has a reduced degree of polarization in a stretch direction than an unstretched material. A method for producing the metallic luster material includes a step of stretching the support holding the organic dye containing no metal element in at least one direction to reduce the degree of polarization in the stretch direction. A method for using the organic dyes containing no metal elements includes stretching the support holding the organic dye in at least one direction, thereby reducing the degree of polarization in the stretch direction.SELECTED DRAWING: Figure 8

Description

[Technical Field]

[0001] The present invention relates to a material that emits a metallic luster, i.e., a metallic luster material, in which a specific organic dye is supported on a support, and more specifically, to a material in which an organic dye that does not contain a metal element is supported on a support, and which emits a metallic luster or whose metallic luster appearance is enhanced by stretching the material. The present invention also relates to a method for producing the metallic luster material and a method for using the organic dye to produce a metallic luster. [Background technology]

[0002] Metals have a unique luster resulting from direct reflection of light from a light source, i.e., metallic luster, which gives a sense of luxury and solidity, and therefore color materials and decorative sheets with metallic luster are used in various fields where design, etc. are required. For example, Patent Document 1 describes a decorative member that expresses the texture of metal.

[0003] However, in recent years, there has been a growing demand for materials and paints that do not contain metal elements, due to a number of reasons to address environmental issues caused by the use of metals, such as corrosion of metal powder in paints, high specific gravity, and unsuitability for use in inkjet printers.

[0004] In addition to metallic substances, there are other materials that have a regular structure or that have a luster due to the reflection of organic pigments, such as opal, jewel beetle, and safflower pigment. In particular, safflower pigment films are known to have a luster similar to that of metal (metallic luster) despite not containing metallic elements. However, because safflower pigment is extracted from the safflower plant, its supply and cost are issues. Furthermore, materials that have a luster other than these metallic substances have a higher degree of polarization compared to true metallic luster, and the texture is different from that of metallic luster. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2019-111834 Summary of the Invention [Problem to be solved by the invention]

[0006] In view of the above technical background, an object of the present invention is to provide a novel material (metallic luster material) that uses an organic dye that does not contain metal elements and that emits a metallic luster. Another object of the present invention is to provide a method for producing the novel metallic luster material. A further object of the present invention is to provide a novel method for using the organic dye that does not contain metal elements and that produces a metallic luster. [Means for solving the problem]

[0007] As a result of extensive research, the inventors discovered that stretching a material in which an organic dye that does not contain metal elements is supported on a support reduces the degree of polarization in the stretching direction of the material, and thus completed the present invention. That is, the present invention and its preferred embodiments relate to the following [1] to

[16] , but are not limited to these. [1] A metallic luster material in which an organic dye containing no metal element is supported on a support, the material is stretched in at least one direction and has a reduced degree of polarization in the stretch direction compared to the unstretched material; Metallic luster material. [2] The organic dye is It is a planar molecule in which the atoms in the chemical structure involved in color development exist on the same plane, and the direction of the transition dipole moment of the chemical structure involved in color development is not fixed to one direction. [1] The metallic luster material described in [1]. [3] The metallic luster material according to [1] or [2], wherein the organic dye is crystal violet. [4] The metallic luster material according to any one of [1] to [3], wherein the stretching is performed at a stretching ratio in the range of 120% to 180%. [5] The metallic lustrous material according to any one of [1] to [4], wherein the support contains a resin. [6] A decorative sheet comprising the metallic luster material according to any one of [1] to [5]. [7] A step of supporting an organic dye containing no metal element on a support to form a support on which the organic dye is supported; and stretching the support carrying the organic dye in at least one direction, thereby reducing the degree of polarization in the stretching direction; A method for producing a metallic luster material, comprising: [8] The organic dye is It is a planar molecule in which the atoms in the chemical structure involved in color development exist on the same plane, and the direction of the transition dipole moment of the chemical structure involved in color development is not fixed to one direction. [7] A method for producing a metallic luster material according to the present invention. [9] The method for producing a metallic luster material according to [7] or [8], wherein the organic dye is crystal violet.

[10] The method for producing a metallic luster material according to any one of [7] to [9], wherein the stretching is performed at a stretching ratio in the range of 120% to 180%.

[11] The method for producing a metallic lustrous material according to any one of [7] to

[10] , wherein the support contains a resin.

[12] A method for using an organic pigment that does not contain metal elements to produce a metallic luster, comprising: A method comprising: supporting the organic dye on a support; stretching the support on which the organic dye is supported in at least one direction; and thereby reducing the degree of polarization in the stretching direction.

[13] The organic dye is It is a planar molecule in which the atoms in the chemical structure involved in color development exist on the same plane, and the direction of the transition dipole moment of the chemical structure involved in color development is not fixed to one direction.

[12] The method described in

[12] .

[14] The method according to

[12] or

[13] , wherein the organic dye is crystal violet.

[15] The method according to any one of

[12] to

[14] , wherein the stretching is performed at a stretching ratio in the range of 120% to 180%.

[16] The method according to any one of

[12] to

[15] , wherein the support comprises a resin. Regarding. [Effects of the Invention]

[0008] The metallic luster material of the present invention is an organic pigment that does not contain metal elements, but emits a luster similar to that of a metal, and therefore can be used in various fields where metallic luster design is required. Furthermore, since an organic pigment that does not contain metal elements is used, it is possible to address environmental issues. Furthermore, compared to safflower pigments and the like, it can be supplied at low cost or stably, and therefore can be used in various fields where metallic luster design is required. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a schematic diagram showing a reflectance spectrum measuring device in an embodiment of the present invention. [Figure 2] 1 is a graph showing the specular reflectance spectrum of Sample 1 at a stretch ratio of 100%. [Figure 3] 1 is a graph showing the specular reflectance spectrum of Sample 2 at a stretch ratio of 100%. [Figure 4] 1 is a graph showing the reflectance in an unpolarized state and the polarized reflectance of Sample 1 at 530 nm when the angle of incidence is changed. [Figure 5] 10 is a graph showing the reflectance in an unpolarized state and the polarized reflectance of Sample 2 at 600 nm when the angle of incidence is changed. [Figure 6] 1 is a graph showing the degree of polarization when the stretching ratio of Sample 1 is changed at an incident angle of 55°. [Figure 7] 1 is a graph showing the degree of polarization when the stretching ratio of Sample 2 is changed at an incident angle of 55°. [Figure 8] These are photographs of Sample 1. (a) is a photograph at a stretch ratio of 100%. (b) is a photograph taken through a polarizing filter at a stretch ratio of 100%. (c) is a photograph at a stretch ratio of 120%. (d) is a photograph at a stretch ratio of 160%. (e) is a photograph at a stretch ratio of 180%. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention provides A metallic luster material in which an organic dye containing no metal element is supported on a support, the material is stretched in at least one direction and has a reduced degree of polarization in the stretch direction compared to the unstretched material; Metallic luster materials.

[0011] Metallic luster The metallic luster material of the present invention is a material that has a luster similar to that of a metal, that is, a metallic luster.

[0012] Metallic luster occurs when metals strongly absorb or reflect light in the visible light range. The sense of luster can also be attributed to binocular parallax, making it difficult to define precisely with numerical values, but generally, the sense of metallic luster is stronger when the reflectivity and directionality are high and the degree of polarization is low. A particularly distinctive feature of metallic luster is that it is not polarized.

[0013] On the other hand, the metallic luster emitted by the metallic luster material of the present invention is generated by the resonance of the vibration of the dye bond electrons with the electromagnetic wave and the subsequent re-emission. The vibration direction of the bond electrons is related to the transition dipole moment and is determined by the molecular shape and orientation of the dye.

[0014] The metallic luster material of the present invention can have a luster that is closer to that of real metal as the degree of polarization is smaller. The degree of polarization (DOP) in the present invention is measured and calculated by the following formula at the angle at which the P-polarized light reflectance is minimum, i.e., the angle at which polarized light is strongly observed.

number

[0015] organic dye The organic dye used in the metallic luster material of the present invention is an organic dye that does not contain a metal element. In one embodiment, the organic dye used in the metallic luster material of the present invention is a planar molecule in which the atoms in the chemical structure responsible for color development are on the same plane, and the transition dipole moment of the chemical structure responsible for color development does not point in a single direction. In another embodiment, the organic dye used in the metallic luster material of the present invention is crystal violet (CV).

[0016] In the present invention, a planar molecule refers to one in which atoms in the chemical structure involved in the color development of the organic dye are present on the same plane. Color development occurs when the transition dipole moment is not zero, i.e., when the transition is allowed, due to the absorption and emission of light accompanying the transition. Therefore, the chemical structure involved in color development refers to a portion in which the transition dipole moment is not zero. Therefore, from the perspective of maintaining the organic dye on the support, as will be described later, if the organic dye has functional groups, etc., atoms in the chemical structure that are not involved in the color development of the functional groups, etc., do not necessarily need to be present on the same plane.

[0017] In addition, the organic dye in the present invention is preferably a planar molecule in which the transition dipole moment of the chemical structure involved in color development is not oriented in a single direction. Specific examples of such organic dyes include fuchsin and crystal violet, which are triphenylmethane-type organic molecules. Crystal violet (CV) shown below is particularly preferred. [ka]

[0018] On the other hand, specific examples of organic dyes that are planar molecules but in which the transition dipole moment of the chemical structure involved in color development is oriented in one direction include cyanine dyes (CY), such as the following 3,3'-dipropylthiadicarbocyanine iodide, which are linear molecules. [ka]

[0019] support The support used in the metallic luster material of the present invention can retain an organic dye. Retaining an organic dye means chemically or physically fixing the organic dye to the surface and / or interior of the support. Methods for retaining an organic dye on the support include, for example, impregnating or coating the support with a solution in which the organic dye is dissolved.

[0020] The material and shape of the support in the present invention are not particularly limited as long as they are stretchable, but for example, those containing a resin are preferred. Examples of materials constituting the support include films and / or sheets of acrylic, olefin, polycarbonate, vinyl chloride, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), nylon, urethane, polyether ether ketone (PEEK), rubber, ion exchange resin, etc. From the viewpoint of chemically retaining the organic dye, ion exchange resin is more preferred, and proton-conductive polymer membranes are particularly preferred. Furthermore, the support is preferably in the form of a film or sheet. Its thickness can be appropriately selected depending on the application, but may be, for example, about 10 μm to 1 cm. It may be more preferably about 100 to 300 μm. It may particularly preferably be about 200 μm.

[0021] stretching The metallic luster material of the present invention can reduce the degree of polarization in the stretching direction by stretching, and the reduction in the degree of polarization by stretching can produce a luster that is closer to a metallic luster. To achieve a metallic luster, the metallic luster material needs to be stretched in at least one direction, but it may also be stretched in multiple directions depending on the application of the metallic luster material. In the present invention, the stretching direction refers to the intended stretching direction when a force is applied to the entire metallic luster material to stretch the entire metallic luster material, and the non-stretching direction refers to the direction perpendicular to the stretching direction. As the entire metallic luster material is stretched, stretching or shrinkage may occur locally in directions deviating from the intended stretching direction, and therefore changes in the degree of polarization may occur in directions other than the intended stretching direction.

[0022] The degree of polarization after stretching is preferably 80% or less, more preferably 75%, and particularly preferably 70% or less. Because metallic luster is not polarized, the lower the degree of polarization, the closer the texture of real metal becomes.

[0023] When the metallic lustrous material of the present invention is stretched, the absorption cross section temporarily increases, and the reflectance increases. On the other hand, as the stretching progresses further, the intermolecular distance of the dye held on the support increases, and the transmitted light increases, and the reflectance decreases.

[0024] The stretching can be performed so that the stretching ratio is greater than 100% and up to 180%, with the length of the metallic luster material in a state where it is stretched to a flat surface before stretching being defined as 100%. The stretching ratio is preferably 120% to 180%. The stretching ratio is more preferably 130% to 160%. The stretching ratio is particularly preferably 140%. When the stretching ratio is 120% or more, the metallic luster can be more clearly perceived. Furthermore, when the stretching ratio is 180% or less, the decrease in reflectance is suppressed and the metallic luster can be more clearly perceived.

[0025] In addition, in organic dyes in which the transition dipole moment of the chemical structure involved in color development is oriented in one direction, the dye molecules become oriented by stretching, increasing the degree of polarization, which can weaken the metallic luster.

[0026] The stretching method is not particularly limited, and depending on the type of support, heating may be performed as appropriate during stretching. Heating may be performed at a temperature of, for example, 300° C. or less, 200° C. or less, or 100° C. or less. Depending on the type of support, stretching may also be performed at room temperature.

[0027] The method for producing a metallic lustrous material of the present invention includes the following steps. A step of supporting an organic dye containing no metal element on a support to form a support supporting the organic dye; and A step of stretching the support carrying the organic dye in at least one direction, thereby reducing the degree of polarization in the stretching direction.

[0028] The step of forming a support carrying an organic dye that does not contain a metal element by supporting the organic dye on the support can be, for example, by impregnating the support with a solution in which the organic dye is dissolved in a solvent, or by applying the solution to the support, etc. The step may also include washing off excess organic dye from the impregnated or coated support and drying the support.

[0029] The solvent is not particularly limited as long as it can dissolve the organic dye, and examples thereof include ethanol, methanol, tetrahydrofuran (THF), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), diethyl ether, ethyl acetate, toluene, etc. The concentration of the solution is not particularly limited, and is preferably, for example, 0.01 mol / L to 0.1 mol / L, and more preferably 0.05 mol / L.

[0030] When the organic dye is retained on the support by impregnation, the impregnation time is not particularly limited as long as the organic dye is sufficiently retained on the support, but may be, for example, 48 hours to 240 hours, more preferably 72 hours to 180 hours, and particularly preferably 96 hours to 120 hours, depending on the organic dye and support used.

[0031] When the organic dye is to be held on the support by coating, it can be coated by a method for coating a normal paint, such as by roller, spray, or ink jet.

[0032] The method for drying the support is not particularly limited, but for example, the support may be naturally dried at room temperature for about 1 hour to 24 hours.

[0033] Examples of the process of stretching the support carrying the organic dye in at least one direction to thereby reduce the degree of polarization in the stretching direction include fixing the support to a jig and stretching one or both ends or the periphery, or placing the cylindrical support in a mold and blowing air into it from the inside to expand it, known as blow molding. Furthermore, appropriate heating may be performed during stretching. For example, when a thermoplastic resin is used for the support, the heating temperature can be adjusted according to the softening point temperature of the resin, and may vary depending on the type of support, but may be 300°C or less, 200°C or less, or 100°C or less. Depending on the type of support, stretching may also be performed at room temperature. The stretching time is not particularly limited as long as the support can be stretched to the desired stretch ratio, but may be, for example, 1 second or less, 1 minute or less, or 1 hour or less.

[0034] The method of using the metal-free organic dye of the present invention to produce a metallic luster involves supporting the organic dye on a support and stretching the support with the organic dye in at least one direction, thereby reducing the degree of polarization in the stretching direction. By reducing the degree of polarization, the metallic luster produced by the organic dye becomes closer to the texture of the luster of a real metal.

[0035] The metallic luster material of the present invention has a low environmental impact because it uses an organic dye that does not contain metal elements, and can be supplied stably at a relatively low cost, so it can be used in a variety of fields. Applications of the metallic luster material of the present invention include, for example, decorative sheets, reflectors, coloring materials, etc. Preferably, it can be used as a decorative sheet. [Example]

[0036] The present invention will be described in detail below with reference to specific examples, but the present invention is not limited to the following examples.

[0037] Example A 0.05 mol / L crystal violet (CV) solution was prepared by dissolving 0.1632 g of CV in 8 mL of ethanol. A 12 mm x 3 mm (200 μm thick) Nafion sheet (Sigma-Aldrich, product name: Nafion 117) was immersed in the prepared CV solution for 103 hours. The sheet was then removed and immersed twice in ethanol to wash off excess dye. The sheet was then dried and designated Sample 1.

[0038] Comparative Example A 0.01 mol / L CV solution was prepared by dissolving 0.054 g of 3,3'-dipropylthiadicarbocyanine iodide (CY) in 10 mL of ethanol. A 1.2 mm x 30 mm (200 μm thick) Nafion sheet (Sigma-Aldrich, product name: Nafion 117) was immersed in the prepared CV solution for 65 hours. The sheet was then removed and immersed twice in ethanol to wash off excess dye. The sheet was then dried and designated Sample 2.

[0039] Measurement of stretch ratio Samples 1 and 2 were fixed to a stretching jig, and the length of the sheet in the state where the sheet was stretched until the entire sheet was flat was used as the reference length, and the stretching ratio was set to 100%.

[0040] Reflectance spectrum measurement The spectral distribution of specular reflectance was measured with the sample fixed to the stretching jig using a fiber optic spectrometer equipped with a tungsten white light source, as shown in Figure 1. To investigate the polarization components, two polarizing plates were inserted between the light source and the detector. The reflectance of only S-polarized light from the light source was set to 100%. The reflectance spectrum of S-polarized light was measured at angles of 10°, 20°, 30°, 40°, 50°, and 60° in Figure 1. The reflectance spectrum of P-polarized light was measured in the same manner as the S-polarized light, with the reflectance of only P-polarized light set to 100%. The specular reflectance spectra of Sample 1 and Sample 2 at a stretch ratio of 100% are shown in Figures 2 and 3.

[0041] For sample 1, shoulders were observed at wavelengths of maximum specular reflectance near 530 nm and 630 nm (Figure 2). For sample 2, shoulders were observed at wavelengths of maximum specular reflectance near 600 nm (Figure 3). The following measurements were made to determine the reflectance related to the gloss of each sample at 530 nm for sample 1 and 600 nm for sample 2.

[0042] Reflectance and polarized reflectance measurements The reflectance in the unpolarized state and the polarized reflectance were measured at 530 nm for Sample 1 and 600 nm for Sample 2 by varying the angle θ in Figure 1. The measurement results for each sample are shown in Figures 4 and 5. For Sample 1, the P-polarized reflectance was at its minimum between 50° and 55°, indicating that polarized light was strongly present (Figure 4). For Sample 2, the P-polarized reflectance was also at its minimum between 50° and 55° (Figure 5).

[0043] Measurement of the degree of polarization The degree of polarization (DOP: Degree of Polarization) of each sample at θ of 55° in Figure 1 was measured while changing the stretching ratio. The degree of polarization ρ was calculated using the following formula.

number

[0044] Figure 6 shows that the degree of polarization in the stretching direction of the metallic luster material using CV decreases with stretching, while Figure 7 shows that the degree of polarization in the stretching direction of the material using CY increases.

[0045] Figure 8 shows photographs of Sample 1. (a) is a photograph taken at a stretch ratio of 100%. (b) is a photograph taken through a polarizing filter at a stretch ratio of 100%. (c) is a photograph taken at a stretch ratio of 120%. (d) is a photograph taken at a stretch ratio of 160%. (e) is a photograph taken at a stretch ratio of 180%. Comparing (a) and (b) in Figure 8, it can be seen that the gloss does not disappear even when viewed through a polarizing filter, and the gloss is close to that of a metal. [Industrial Applicability]

[0046] The metallic luster material of the present invention has a small environmental impact and can be supplied stably at a relatively low cost, and therefore has high potential for use as a substitute for decorative sheets containing metal in home appliances, office equipment, automobile parts, etc.

Claims

1. A metallic luster material comprising an organic dye supported on a support, the organic dye containing no metal element, the organic dye being a planar molecule in which atoms in the chemical structure involved in color development are present on the same plane, and the transition dipole moment of the chemical structure involved in color development does not have a fixed direction, the organic dye and the support supporting the organic dye are stretched in at least one direction at a stretching ratio in the range of 120% to 180%, so that the degree of polarization in the stretching direction is 80% or less of the degree of polarization of the unstretched material; Metallic luster material.

2. The metallic luster material according to claim 1 , wherein the organic pigment is crystal violet.

3. The metallic lustrous material according to claim 1 or 2, wherein the support comprises a resin.

4. A decorative sheet comprising a metallic luster material described in any one of claims 1 to 3.

5. a step of supporting an organic dye on a support, the organic dye being a planar molecule that does not contain metal elements, in which atoms in the chemical structure involved in color development are present on the same plane, and in which the direction of the transition dipole moment of the chemical structure involved in color development is not fixed to one direction; and a step of reducing the degree of polarization in the stretching direction by stretching the organic dye and the support carrying the organic dye at a stretching ratio in the range of 120% to 180% in at least one direction, so that the degree of polarization in the stretching direction is 80% or less of the degree of polarization of the unstretched material; A method for producing a metallic luster material, comprising:

6. 6. The method for producing a metallic lustrous material according to claim 5, wherein the organic dye is crystal violet.

7. The method for producing a metallic lustrous material according to claim 5 or 6, wherein the support comprises a resin.

8. A method for using an organic dye that produces metallic luster, does not contain metal elements, is a planar molecule in which atoms in the chemical structure involved in color development exist on the same plane, and the direction of the transition dipole moment of the chemical structure involved in color development is not fixed to one direction, The organic dye is supported on a support, and the organic dye and the support supporting the organic dye are stretched in at least one direction at a stretching ratio in the range of 120% to 180%, thereby making the degree of polarization in the stretched direction 80% or less of the degree of polarization of the unstretched material.

9. The method of claim 8 , wherein the organic dye is crystal violet.

10. The method of claim 8 or 9, wherein the support comprises a resin.

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