JP4448926B2 - Colored polymer material phosphorized by laser - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a colored polymer material that has been made fluorescent by irradiation with a laser beam.
[0002]
[Prior art]
In general, in order to cause a colored polymer material that does not exhibit fluorescence emission to emit fluorescence, a fluorescent whitening agent or a fluorescent pigment such as a fluorescent pigment is added to the polymer material, followed by molding. However, since the fluorescent light emitting material is expensive, there is a problem in that many material costs are required.
[0003]
A fluorescent substance can also be formed by adding a functional group that expresses fluorescent emission to a part of the chemical structure of the polymer and then performing molding processing. In order to change the structure, the properties of the original polymer are lost. In addition, there is a drawback that the running cost for manufacturing is high.
[0004]
Furthermore, since the fluorescent substances obtained from these conventional methods are all fluorescent in the polymer portion, the fluorescent emission cannot be expressed partially and at a designated place.
[0005]
[Problems to be solved by the invention]
As described above, in order to cause a colored polymer material that does not exhibit fluorescence emission to emit fluorescence, a fluorescent light emitting material such as a fluorescent brightening agent or a fluorescent pigment is added to the polymer material, and then molding processing is performed. Alternatively, a method of performing molding after adding a functional group that expresses fluorescence emission to a part of the chemical structure of the polymer is used. There is a problem that the cost is high in terms of manufacturing and manufacturing. In order to solve the above problems, the present inventors first irradiate the surface of a polymer material that does not exhibit fluorescence as a base material with a laser beam, and then irradiate the surface of the polymer material with ultraviolet rays. The composition of the polymer material that exhibits fluorescence emission that develops color in the visible light region was clarified and was filed as “polymer material that exhibits fluorescence emission by laser irradiation” (Japanese Patent Application No. 11-307030). The present inventors have further researched and irradiated a laser beam on the surface of a colored polymer material obtained by mixing an organic pigment and a polymer material as a base material, and then irradiated the surface with ultraviolet rays. A colored polymer material that develops color is provided.
[0006]
[Means for Solving the Problems]
The present invention has been made to solve the above-described problems. The surface of a colored polymer material obtained by mixing an organic pigment and a polymer material is changed by irradiation with a laser beam, and is converted into a fluorescent material. It is a molecular material, and when the phosphorized surface is irradiated with ultraviolet rays, a laser beam irradiation surface of the colored polymer material develops a color in the visible light region, and is made fluorescent with a laser. Colored polymer material.
[0007]
The colored polymer material of the present invention is such that when the surface is irradiated with a laser beam, the polymer material is decomposed by the laser beam, and a part of the decomposition product is added to the organic pigment for coloring. It is a colored polymer material fluorescentized with a characteristic laser.
[0008]
Further, the present invention is a colored polymer material fluorescentized with a laser, which is a mixture of a compound having an ester bond that generates a carboxyl group by decomposition and a condensed polycyclic organic pigment.
[0009]
Further, it is a colored polymer material fluorescentized with a laser, which is a mixture of a polymer material that forms a polyene structure by decomposition and a condensed polycyclic organic pigment.
[0010]
The compound containing an ester bond that generates a carboxyl group by decomposition is a polyester resin, an unsaturated polyester resin, an alkyd resin, an acrylic resin, a polycarbonate, a cellulose acetate, a urethane resin, or a polyamide resin. Unsubstituted quinacridone, quinacridone magenta, quinacridone scarlet, quinacridone maroon, dichloroquinacridone magenta, carbazole violet, perinone orange, perinone red, perylene vermillion, perylene red BL, perylene maroon, perylene red, perylene violet, indigo blue, thioindigo Colored phosphors that have been fluorescentized with one or more of the group consisting of magenta, thioindigo Bordeaux or DPP red It is a child material.
[0011]
In addition, as a compound that generates a polyene structure by decomposition, there are polyvinyl chloride resin, polyvinyl acetate resin, and polyvinyl alcohol. As condensed polycyclic organic pigments, unsubstituted quinacridone, quinacridone magenta, quinacridone scarlet, quinacridone maroon, dichloromethane. Of the group consisting of lasers that are quinacridone magenta, carbazole violet, perinone orange, perinone red, perylene vermillion, perylene red BL, perylene maroon, perylene red, perylene violet, indigo blue, thioindigo magenta, thioindigo Bordeaux or DPP red It is a colored polymer material that is made into a phosphor by one kind or two or more kinds.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
As a result of repeated research, the colored polymer material that becomes a phosphor by laser irradiation of the present invention is decomposed on the surface of the colored polymer material when the surface of the colored polymer material is irradiated with a laser beam. Alternatively, a polyene structure is formed, a part of which is combined with an organic pigment for coloring. By this mechanism, when the bonding part is irradiated with ultraviolet rays, a combination of a polymer material that develops color in the visible light region and an organic pigment, that is, a polymer material having an ester bond that generates a carboxyl group by decomposition or a polyene structure by decomposition. It was found to be a mixture of the resulting polymer material and condensed polycyclic organic pigments.
[0013]
Since these polymer materials emit fluorescent light only by irradiating a laser, the material cost of additives such as fluorescent pigments is not required, and the running cost is hardly required. In addition, since a part of the polymer decomposition component is added to the organic pigment only on the surface, the structural change does not occur inside the colored polymer material, so that the colored polymer material itself does not deteriorate or change in properties. Furthermore, by applying energy from a laser beam only to a specific location, it is possible to cause fluorescence emission at a specified location on the surface of the colored polymer material, so laser irradiation that can be applied to counterfeiting and tampering prevention is possible. Is a polymer material that exhibits fluorescence emission.
[0014]
【Example】
(Example 1) Hereinafter, the present invention will be described based on examples, but the present invention is not limited to these examples.
[0015]
The surface of the polyester resin to which 1% of quinacridone magenta is added is irradiated while changing the output of the CO2 laser stepwise. Next, FIG. 1 shows the fluorescence intensity at a wavelength of 548 nm when the laser irradiation surface is irradiated with 365 nm ultraviolet rays. The fluorescence intensity suddenly increased at a laser output of 1.7 W or higher, reached a maximum at a laser output of 2.2 W, and decreased at a laser output thereafter.
[0016]
Next, each sample was chemically modified in trifluoroethanol in the gas phase in order to determine the amount of carboxyl groups on the surfaces of the polyester resin and 1% quinacridone magenta polyester resin irradiated by laser with each output. By this method, trifluoroethanol reacts selectively with carboxyl groups to produce trifluoroethyl ester. The surface of the sample chemically modified with trifluoroethanol is subjected to X-ray photoelectron spectroscopy (ESCA) to determine the spectral intensities of F1s (photoelectrons emitted from the 1s orbit of fluorine) and C1s (photoelectrons emitted from the 1s orbit of carbon). FIG. 2 shows the results of measurement and the amount of carboxyl group determined as the relative intensity of fluorine to carbon (F1s / C1s).
[0017]
In the case of polyester resin, the relative strength (F1s / C1s) increases rapidly when the laser output is 1.7W or higher, and becomes maximum when the laser output is 2.2W. The relative strength (F1s / C1s) decreases at the laser output after that. did. This indicates that the ester bond of the polyester was decomposed by laser irradiation to generate a carboxyl group (FIG. 3). However, in the case of a polyester resin containing quinacridone magenta, the change in relative strength (F1s / C1s) due to laser irradiation was small compared to the case of the polyester resin alone. This is probably because some of the carboxyl groups generated by the decomposition of the polyester resin are bonded to quinacridone magenta. As a result of this structural change, it is presumed that fluorescence emission was developed. FIG. 4 shows an expected structural formula of the binding portion between the generated carboxyl group and quinacridone magenta.
[0018]
Furthermore, as a result of analyzing the laser irradiated portion by nuclear magnetic resonance (NMR) and infrared spectroscopy (IR), no structural change was observed from the obtained spectra. However, considering that the measurement by ESCA can obtain information on the outermost surface having a depth of several nanometers from the surface, the structural change occurs only on the surface of the polymer material by laser irradiation. That is, it is clear from these results that there is no structural change inside.
[0019]
(Example 2) The surface of a polyvinyl chloride resin to which 1% of quinacridone magenta is added is irradiated with a CO2 laser while changing the output stepwise. Next, FIG. 5 shows the fluorescence intensity at a wavelength of 522 nm when the laser irradiation surface is irradiated with 365 nm ultraviolet rays. The fluorescence intensity suddenly increased at a laser output of 12.0 W or more, reached a maximum at a laser output of 19.2 W, and the fluorescence intensity decreased at the laser output thereafter. This phenomenon was thought to be because the polyvinyl chloride resin was dehydrochlorinated by the heat of the laser to produce a polyene structure, and a part of the polyene structure was added to quinacridone magenta as in Example 1.
[0020]
As is clear from the above examples, according to this example, partial fluorescence can be expected, so that counterfeiting and falsification of high value-added products such as banknotes, stock certificates, and securities such as bonds can be prevented. Applicable. It can also be applied as a personal identification method for cards. Furthermore, since no fluorescent agent or the like is added, the material cost is only the organic pigment and polymer material cost, so the running cost is also reduced.
[0021]
【The invention's effect】
As described in detail above, the present invention is a coloring in which a polymer material is decomposed by applying laser energy, a part of the decomposition product is added to an organic pigment, and color is developed in the visible light region when irradiated with ultraviolet rays. Since the present invention relates to a polymer material and can emit fluorescence only at a specific location, it can be designed as a fluorescence emission image. Moreover, since these reactions are chemical changes that occur on the surface of the colored polymer material, they do not cause changes in the chemical structure inside the polymer material. Therefore, there is almost no change in the properties of the polymer material before processing, and there is no restriction on the intended use.
[Brief description of the drawings]
FIG. 1 is a graph showing the relationship between the fluorescence emission intensity at 548 nm when a quinacridone magenta-added 1% polyester resin surface subjected to laser irradiation while changing the laser output stepwise is irradiated with 365 nm ultraviolet rays.
[Fig. 2] Polyester resin and laser resin irradiated with 1% quinacridone magenta added to the polyester resin stepwise by changing the laser output were chemically modified in the gas phase with trifluoroethanol, and F1s (fluorine 1s by ESCA) The graph shows the relative intensity (F1s / C1s) of fluorine with respect to carbon by measuring the spectral intensity of photoelectrons emitted from orbits) and C1s (photoelectrons emitted from 1s orbitals of carbon).
FIG. 3 is a view showing a structural formula in which an ester bond of polyester is decomposed by laser irradiation to generate a carboxyl group.
FIG. 4 is a diagram showing an expected structural formula of a binding portion between a generated carboxyl group and quinacridone magenta.
FIG. 5 is a graph showing the relationship between fluorescence emission intensity at 522 nm when irradiating 365 nm ultraviolet rays onto the surface of a polyvinyl chloride resin with 1% quinacridone magenta added with laser irradiation while changing the laser output stepwise.

Claims (4)

The surface of a colored polymer material formed by mixing a polymer material and an organic pigment is a fluorescent polymerized colored polymer material that is changed by irradiation with a laser beam, and the polymer material is irradiated with a laser beam. In the polymer material having an ester bond that generates a carboxyl group by decomposition, and the organic pigment is a condensed polycyclic organic pigment bonded to the decomposed polymer material, and is converted into the phosphor. A laser-fluorinated colored polymer material, wherein when the surface is irradiated with ultraviolet rays, the laser beam irradiation surface of the colored polymer material develops color in the visible light range. The surface of a colored polymer material formed by mixing a polymer material and an organic pigment is a fluorescent polymerized colored polymer material that is changed by irradiation with a laser beam, and the polymer material is irradiated with a laser beam. And the organic pigment is a condensed polycyclic organic pigment that binds to the decomposed polymer material and has ultraviolet rays on the phosphorized surface. A colored polymer material fluorescentized with a laser, characterized in that the surface irradiated with the laser beam of the colored polymer material is colored in the visible light region when irradiated with. The polymer material containing an ester bond that generates a carboxyl group by decomposition is a polyester resin, an unsaturated polyester resin, an alkyd resin, an acrylic resin, a polycarbonate, a cellulose acetate, a urethane resin, or a polyamide resin, and the condensed polycyclic system Unsubstituted quinacridone, quinacridone magenta, quinacridone scarlet, quinacridone maroon, dichloroquinacridone magenta, carbazole violet, perinone orange, perinone red, perylene vermillion, perylene red BL, perylene maroon, perylene red, perylene violet, indigo blue, thio indigo magenta, laser according to claim 1, wherein at least one of the group consisting of thioindigo Bordeaux or DPP Red Hikaritai of the colored polymeric material. Examples of the compound that forms a polyene structure by the decomposition include polyvinyl chloride resin, polyvinyl acetate resin, and polyvinyl alcohol. As the condensed polycyclic organic pigment, unsubstituted quinacridone, quinacridone magenta, quinacridone scarlet, quinacridone maroon, dichloromethane. One of the group consisting of quinacridone magenta, carbazole violet, perinone orange, perinone red, perylene vermillion, perylene red BL, perylene maroon, perylene red, perylene violet, indigo blue, thioindigo magenta, thioindigo Bordeaux or DPP red The colored polymer material phosphorized with a laser according to claim 2, wherein two or more kinds are used.

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