WO2017209224A1

WO2017209224A1 - Method for producing article having metallic luster, and toner for metallic luster colors and printing method using same

Info

Publication number: WO2017209224A1
Application number: PCT/JP2017/020373
Authority: WO
Inventors: 星野　勝義; 輝大水戸川; 宮本克真
Original assignee: 国立大学法人千葉大学
Priority date: 2016-05-31
Filing date: 2017-05-31
Publication date: 2017-12-07

Abstract

Provided are: a novel method for producing an article having metallic luster, wherein a solvent is not used when an article having metallic luster is formed; and a toner for metallic luster colors and a printing method, each of which uses this method. One embodiment of the present invention is a method for producing an article having metallic luster by applying a pressure to a thiophene polymer. In this case, it is preferable that the thiophene polymer is obtained by electropolymerization or chemical polymerization. Another embodiment of the present invention is a toner for metallic luster colors, which contains a thiophene polymer. Another embodiment of the present invention is a printing method, wherein a toner for metallic luster colors, which contains a thiophene polymer, is arranged on an article and the toner for metallic luster colors is fixed thereon by applying a pressure to the toner for metallic luster colors.

Description

A method for producing an article having a metallic luster, a metallic luster color toner using the same, and a printing method.

The present invention relates to a method for producing an article having a metallic luster, a metallic luster toner using the same, and a printing method.

Metals are generally hard and are used not only for parts that require mechanical strength, such as home appliances and automobiles, but also because they have a metallic luster, they are excellent in texture and are used in every kind of everyday life such as furniture and sundries. . Gold is particularly popular because it can give a sense of quality. However, not only is the metal itself expensive, but it is not easy to process, and the metal is expensive.

As means for solving the above-mentioned problems, for example, a metal plating method for coating a metal thin film on the surface of an article such as a polymer or glass, or a paint added with fine particles or flaky metal is applied to the surface of the article. There are surface treatment techniques such as methods. When this technique is used, an article having a metallic luster can be produced at low cost by manufacturing an article with a polymer compound and coating the surface thereof with a metal thin film or a paint containing a metal.

However, the metal plating method has many limitations on the materials that can be surface treated. In addition, the surface technique uses a metal after all, and it is less expensive than the case where the entire article is used with a metal, but it becomes expensive. In particular, the coating material to which the above metal is added has a problem that due to the difference in specific gravity between the polymer binder and the metal in the coating material, the metal particles are settled, and spots are easily formed when the coating film is formed.

Therefore, it is considered that the above problem can be solved if there is a substance exhibiting metallic luster using a substance other than metal. As a technique relating to a non-metallic substance exhibiting metallic luster, for example, the following Patent Document 1 discloses. There are techniques described.

WO2014 / 0231405 gazette

However, the technique described in the above-mentioned Patent Document 1 gives a metallic luster by dissolving in a solvent and uniformly coating on an article, and requires dissolution with a solvent. That is, the range of application is further expanded if a metallic luster can be obtained without using a solvent.

Therefore, in view of the above problems, the present invention provides a method for producing an article having a novel metallic luster that does not use a solvent when forming an article having a metallic luster, and a metallic gloss color toner and a printing method using the same. The purpose is to provide.

The method for producing an article having a metallic luster according to one aspect of the present invention that solves the above-described problems involves pressurizing a thiophene polymer.

In this respect, the thiophene polymer is preferably formed by chemical polymerization or electrolytic polymerization.

Also, the metallic gloss color toner according to another aspect of the present invention contains a thiophene polymer.

Also, a printing method according to another aspect of the present invention is to fix a metallic glossy color toner containing a thiophene polymer on a paper and pressurize the metallic glossy color toner.

As described above, according to the present invention, there is provided a method for producing an article having a new metallic luster that does not use a solvent when forming an article having a metallic luster, and a toner for metallic luster color and a printing method using the same. it can.

It is a figure which shows the outline of the article | item which has the metallic luster which concerns on Embodiment 1. FIG. It is a figure which shows the outline of another example of the articles | goods which have metallic luster concerning Embodiment 1. FIG. It is a figure which shows the image of the manufacturing process of the articles | goods which have a metallic glossy film which concerns on Embodiment 1. FIG. It is a figure which shows the image of the manufacturing process of the articles | goods which have metal luster concerning Embodiment 1. FIG. It is a figure which shows the image of the toner particle which concerns on an application example. It is a figure which shows the image in the case of printing using the toner particle which concerns on an application example. It is a photograph figure of the articles | goods which have the metallic luster produced in the Example. It is a photograph figure of the articles | goods which have the metallic luster produced in the Example. It is a photograph figure of the articles | goods which have the metallic luster produced in the Example. It is a photograph figure of the articles | goods which have the metallic luster produced in the Example. It is a photograph figure of the articles | goods which have the metallic luster produced in the Example. It is a photograph figure of the articles | goods which have the metallic luster produced in the Example. It is a photograph figure of the articles | goods which have the metallic luster produced in the Example. It is a figure which shows the regular reflection spectrum of the articles | goods which have the metallic luster created in the Example. It is a graph which shows the relationship between the pressure applied at the time of pressing, and the maximum reflectance. It is a figure which shows 3D image and arithmetic mean roughness Ra by a laser microscope. It is a figure which shows 3D image and arithmetic mean roughness Ra by a laser microscope. It is a figure which shows 3D image and arithmetic mean roughness Ra by a laser microscope. It is a figure which shows 3D image and arithmetic mean roughness Ra by a laser microscope. It is a figure which shows 3D image and arithmetic mean roughness Ra by a laser microscope. It is a figure which shows 3D image and arithmetic mean roughness Ra by a laser microscope. It is a figure which shows 3D image and arithmetic mean roughness Ra by a laser microscope. It is a figure which shows the relationship between the pressure applied at the time of pressing, and Ra. It is a photograph figure of the film | membrane which has the metallic luster produced by the powder and rubbing of the thiophene oligomer. It is a figure which shows the measurement result of the regular reflection spectrum of the film | membrane produced by rubbing. It is a figure which shows the result of the colorimetry of the film | membrane produced by rubbing. It is a figure which shows the result of the X-ray opening spectrum measurement of the film | membrane produced by rubbing. It is a figure which shows the image of the structure of an edge on lamella and a face on lamella. It is a figure which shows the outline of the article | item which concerns on Embodiment 3. FIG. It is a figure which shows an example of the other shape of the articles | goods which concern on Embodiment 3. FIG. It is a figure which shows the film | membrane produced from the nitromethane solution. It is a figure which shows the film | membrane produced from the GBL solution. It is a figure which shows the regular reflection spectrum of the film | membrane produced from the nitromethane solution. It is a figure which shows the regular reflection spectrum of the film | membrane produced from the GBL solution. It is a chromaticity diagram of a film made from a nitromethane solution. It is a chromaticity diagram of a film made from a GBL solution. It is a figure which shows the difference of the film | membrane produced from the nitromethane solution, and a gold vapor deposition film | membrane. It is a figure which shows the difference of the film | membrane produced from the GBL solution, and a gold vapor deposition film | membrane. It is a figure which shows the color difference of the film | membrane produced from the nitromethane solution, and a gold vapor deposition film | membrane. It is a figure which shows the color difference of the film | membrane produced from the GBL solution, and a gold vapor deposition film. It is a photograph figure of the articles | goods made into the three-dimensional shape which concerns on an Example. It is a photograph figure of the golden tone film produced in the Example. It is a figure which shows the total reflection spectrum of the golden tone film produced in the Example. It is a figure which shows the total reflection spectrum of the golden tone film produced in the Example. It is a figure which shows the total reflection spectrum of the golden tone film produced in the Example. It is a figure which shows the absolute value of the colorimetric data of the gold color tone film produced in the Example. It is a figure which shows the absolute value of the colorimetric data of the gold color tone film produced in the Example. It is a figure which shows the absolute value of the colorimetric data of the gold color tone film produced in the Example. It is a figure which shows the color difference of a gold vapor deposition film | membrane and the gold color tone film | membrane of an Example. It is a figure which shows the color difference of a gold vapor deposition film | membrane and the gold color tone film | membrane of an Example. It is a figure which shows the color difference of a gold vapor deposition film | membrane and the gold color tone film | membrane of an Example. It is a figure which shows the color difference of the gold color tone film | membrane without resin, and the gold color tone film | membrane of an Example. It is a figure which shows the color difference of the gold color tone film | membrane without resin, and the gold color tone film | membrane of an Example. It is a figure which shows the color difference of the gold color tone film | membrane without resin, and the gold color tone film | membrane of an Example. It is a photograph figure of the golden tone film produced in the Example. It is a figure which shows the total reflection spectrum of the golden tone film produced in the Example. It is a figure which shows the absolute value of the colorimetric data of the gold color tone film produced in the Example. It is a figure which shows the color difference of a gold vapor deposition film | membrane and the gold color tone film | membrane of an Example. It is a figure which shows the color difference of the gold color tone film | membrane without resin, and the gold color tone film | membrane of an Example. It is a figure which shows an X-ray diffraction spectrum. It is a wide scan XPS spectrum of the PES front surface and the PMMA back surface. It is an XPS spectrum of the S2p region of the PES front surface and the PMMA back surface. It is the XPS spectrum of the Cl2p area | region of a PES surface and a PMMA back surface.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention can be implemented in many different forms, and is not limited to the following embodiments and examples.

(Embodiment 1)
(Articles with a metallic gloss film)
FIG. 1 is a schematic cross-sectional view of an article (hereinafter referred to as “article having metallic luster”) formed with a film having metallic luster containing a thiophene polymer according to the present embodiment.

Here, the article according to the present embodiment is not particularly limited as long as it has a metallic luster, not only electronic machine parts such as home appliances and automobiles, but also miscellaneous goods, clothes used in daily life such as furniture and toys, Although there are various kinds of paper products and the like, a flat surface is a preferable example from the viewpoint of easily applying pressure evenly. In the example of this figure, an example of paper is shown. Further, as described later, the entire article itself may be an article having a metallic luster.

In the present embodiment, the thickness of the film having a metallic luster is not limited as long as the metallic luster can be exhibited, but if it is 0.1 μm or more, the film having the metallic luster can be obtained. More preferably, the thickness is 0.3 μm or more, and even more preferably 0.6 μm or more, the film has a more sufficient metallic luster.

Further, the film having metallic luster according to the present embodiment includes a thiophene polymer.

In the present embodiment, the “thiophene polymer” refers to a polymer in which two or more thiophenes are bonded to each other and is a compound represented by the following general formula.

In the above formula, R is a substituent and is not limited as long as it can impart a metallic luster to the film, but is not limited to an alkoxy group, an amino group, an alkyl group, a hydroxyl group, a hydroxyalkyl group, an aryl group, a cyano group, Or it is preferable that it is either halogen. R may be one or two per thiophene ring. Moreover, in the thiophene polymer according to the present embodiment, the Rs of the thiophenes may be the same or different.

As is clear from the above description, “thiophene” is a heterocyclic compound containing sulfur, and is a compound represented by the following general formula. In the formula, the definition of R is the same as described above.

In the above formula, when R is an alkoxy group, it is not limited, but the number of carbon atoms is preferably 1 or more and 8 or less, more specifically, 3-methoxythiophene, 3,4-dimethoxy. Examples include thiophene, 3-ethoxythiophene, 3,4-diethoxythiophene, 3-propoxythiophene, 3-butoxythiophene, 3-hydroxythiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene can do.

Further, when R in the above formula is an alkyl group, the number of carbon atoms is preferably 1 or more and 12 or less, more specifically, 3-methylthiophene, 3,4-dimethyl. Thiophene, 3-ethylthiophene, 3,4-diethylthiophene, 3-butylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-octylthiophene, 3-nonylthiophene, 3-decylthiophene, 3-undecylthiophene, Examples thereof include 3-dodecylthiophene and 3-bromo-4-methylthiophene.

In the above formula, when R is an amino group, 3-aminothiophene, 3,4-diaminothiophene, 3-methylaminothiophene, 3-dimethylaminothiophene, 3-thiophenecarboxamide, 4- (thiophene-3- Il) Aniline and the like can be exemplified.

Further, in this embodiment, the molecular weight of the “thiophene polymer” is not limited as long as it can have a metallic luster and can be formed as a film, but is determined by a GPC measurement method. The peak of the weight average molecular weight distribution is preferably in the range of 200 or more and 30000 or less, more preferably in the range of 500 or more and 10,000 or less.

In addition, as described above, the article having a metallic luster according to the present embodiment may be configured by an article including a thiophene polymer having a metallic luster instead of forming a film having a metallic luster on the article surface. It is. Although a manufacturing method will be described later separately, a thiophene polymer may be molded so as to have a desired shape of the article itself to give a metallic luster. As an example of this, an example of a tablet-shaped article is shown in FIG.

(Method for producing an article having metallic luster)
The method for producing an article having a metallic luster made of a thiophene polymer in this embodiment (hereinafter also referred to as “the present method”) is a method in which a thiophene polymer powder is placed on an article and the thiophene polymer is pressurized. is there.

(Chemical polymerization)
In the present embodiment, as described above, the thiophene polymer can also be produced using chemical polymerization. Here, the “chemical polymerization method” refers to polymerization performed in at least one of a liquid phase and a solid phase using an oxidizing agent.

In this embodiment, the reason why the thiophene polymer exhibits a metallic luster is the same as in the case of electrolytic polymerization, but the reason is that the molecules constituting the thiophene polymer are regularly oriented and reflect a specific wavelength. It is believed that there is. This is supported by the fact that the produced film shows a sharp peak in X-ray diffraction. The details will be apparent from the examples described later, but in the X-ray diffraction measurement of the thiophene polymer, there are no halo patterns due to amorphous, and there are three peaks that are considered to be derived from the regular structure of the thiophene polymer. It means that it can be clearly observed in the range of diffraction angle (2θ) from 5 degrees to 30 degrees.

The article in the present embodiment is formed with a film made of the above thiophene polymer. This thiophene polymer is very stable in the air, hardly deteriorates even if left in the air for a long time, and is long. It can show a metallic luster over time.

Here, a method for producing a film having metallic luster using the chemical polymerization method in the present embodiment (hereinafter simply referred to as “the present method”) will be described.

This method includes (1) a step of polymerizing thiophene using an oxidizing agent to obtain a solution containing a thiophene polymer, and (2) a step of removing the solution containing the thiophene polymer to obtain a thiophene polymer powder. . That is, in this embodiment, chemical polymerization is performed to produce a thiophene polymer.

First, in this method, (1) thiophene is polymerized using an oxidizing agent, and a solution containing this thiophene polymer is prepared. The “thiophene” used here and the resulting “thiophene polymer” are those described above. As described above, the thiophene polymer is preferably in the range of a so-called oligomer, and specifically, the polymerization is preferably performed so that the distribution peak of the weight average molecular weight is in the range of 200 to 30000.

In this step, the oxidizing agent is not limited as long as the thiophene polymer can be produced, and various ones can be used. For example, ferric salt, cupric salt, cerium salt, dichromic acid Examples thereof include salts, permanganate, ammonium persulfate, boron trifluoride, bromate, hydrogen peroxide, chlorine, bromine and iodine. Among them, ferric salt is preferable. Hydrates may also be used. In this case, the pair of ions can be appropriately adjusted and is not limited. For example, chloride ion, citrate ion, oxalate ion, p-toluenesulfonate ion, perchlorate ion, hexachlorate ion, Fluorophosphate ion, tetrafluoroborate ion, and the like. Among them, when at least one of perchlorate ion, hexafluorophosphate ion, and tetrafluoroborate ion is used, a metal close to gold Gloss can be obtained, which is preferable. The reason why a metallic luster close to gold can be obtained is speculated, but perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion is incorporated as a dopant in the thiophene polymer during polymerization, This is thought to be due to binding to and stabilizing the cation moiety generated in the thiophene polymer, and contributing to the formation of an ordered structure. In fact, when films having metallic luster are analyzed, it has been confirmed that they exist stably.

In this step, the polymerization is preferably performed in a solvent using a solvent. The solvent to be used is not limited as long as the oxidizing agent and thiophene can be sufficiently dissolved and polymerized efficiently, but the organic solvent has a high polarity and a certain degree of volatility. Preferably, for example, acetonitrile, nitromethane, γ-butyrolactone, propylene carbonate, nitromethane, 1-methyl-2-pyrrolidinone, dimethyl sulfoxide, 2-butanone, tetrahydrofuran, acetone, methanol, anisole, chloroform, ethyl acetate, hexane, trichloroethylene, cyclohexanone, Dichloromethane, chloroform, dimethylformamide, ethanol, butanol, pyridine, dioxane, and mixtures thereof can be used, but acetonitrile, nitromethane, γ-butyrolactone, carbonate Lopylene is preferable because it has a soluble thiophene polymer and tends to form a film with better metallic luster.

In this step, the amount of thiophene and oxidizing agent used for the solvent can be adjusted as appropriate and is not limited. However, when the weight of the solvent is 1, the weight of thiophene is 0.00007 or more and 7 or less. More preferably, it is 0.0007 or more and 0.7 or less, and in the case of iron (III) perchlorate n hydrate, the weight is preferably 0.0006 or more and 6 or less, more preferably 0. 0.006 or more and 0.6 or less.

In this step, the ratio of the thiophene to the oxidizing agent used is preferably 0.1 or more and 1000 or less, and more preferably 1 or more and 100 or less, when the weight of thiophene is 1.

In this step, thiophene and oxidant may be added to the solvent all at once, but two types of solutions are separately prepared: a solution in which thiophene is added to the solvent and a solution in which the oxidant is added to the solvent. The polymerization reaction may be performed by combining them.

In the present method, the thiophene polymer produced as described above is preferably prepared as a powdered thiophene polymer (thiophene polymer powder) by removing the solvent. In this way, an article having a metallic luster can be easily produced only by pressing. When an oxidizing agent containing the above-mentioned perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, or chloride ion is used, it remains stably because it is stably bonded to the polymer. This state can be stably maintained.

(Electropolymerization)
In the present embodiment, electrolytic polymerization is a method of dissolving a solution insoluble polymer film on a conductor by dissolving a substance (monomer) that is a precursor of a polymer in a solution containing a supporting electrolyte, and then subjecting the monomer to electrode oxidation. The technique to form.

In this embodiment, it is preferable to use a potential sweep method when anodizing. The potential sweep method is a treatment in which a pair of electrodes is immersed in a solution containing a supporting electrolyte and applied while changing the potential at a constant rate.

The solvent of the solution used in this embodiment is not particularly limited. For example, in addition to water and alcohol, Akira Fujishima, Masuo Aizawa, Satoru Inoue, Electrochemical Measurement, Gihodo Publishing, Vol. 107-114 Page, 1984 can be used. A mixed solvent of various solvents is also preferable.

Further, the supporting electrolyte of the solution used in the present embodiment is an essential component in electrolysis, and preferably has a cation or an anion that is sufficiently dissolved in a solvent and hardly electrolyzed, and is not limited thereto. However, it is preferable to use at least one of lithium salt, sodium salt, potassium salt, calcium salt, and tetraalkylammonium salt if attention is paid to cations, and halide, sulfate, nitrate, phosphoric acid, etc. if attention is paid to anions. It is preferable to use at least one of a salt, a perchlorate, a boron trifluoride salt, and a hexafluorophosphate. The concentration of the supporting electrolyte is not limited, but is preferably 0.001 M or more and solubility or less, and more preferably 0.01 M or more and 1 M or less.

In the present embodiment, the concentration of the thiophene monomer used in the electrolytic polymerization in the electrolytic solution is not limited, but is preferably 0.1 mM or more and less than or equal to the solubility, and more specifically 1 mM or more and 1M. The following is more preferable.

In this embodiment, the electropolymerization is performed by immersing a conductor (functioning as an operating electrode) in an electrolytic container containing a solution, and counter electrodes, and if necessary, three electrodes of a reference electrode serving as a potential reference Can be employed, or a two-electrode system using only a conductor and a counter electrode can be employed. Note that the three-electrode system that can strictly regulate the electric potential of the conductor with respect to the reference electrode as a reference is used to produce an article having a metallic luster that contains the thiophene polymer formed by this method with good reproducibility. Is more preferable in that

The conductor as the working electrode is not limited as long as it is a substance that is stable against electrode oxidation in both the three-electrode type and the two-electrode type. For example, as described above, A transparent glass electrode, a metal electrode, a glassy carbon electrode or the like coated with indium tin (hereinafter abbreviated as “ITO”) or tin oxide can be suitably used. Moreover, as a counter electrode, in addition to the electrode material, a metal electrode such as stainless steel or a copper plate can be suitably used. The reference electrode is not limited, but for example, a silver / silver chloride electrode (Ag / AgCl electrode) or a saturated calomel electrode can be preferably used.

In the present embodiment, the potential sweep method in the electropolymerization is preferably sweeping between a negative potential and a positive potential. In this case, the negative potential is preferably in the range of −1.5V to −0.01V, more preferably in the range of −1.0V to −0.1V, and still more preferably −0.7V. It is the range of -0.2V or less. The positive potential is preferably in the range of + 1.0V to + 3.0V, more preferably in the range of + 1.0V to + 2.0V, and still more preferably in the range of + 1.0V to + 1.5V. It is.

In the present embodiment, the potential sweep method is not limited as long as the sweep rate can produce an article having a metallic luster, but within a range of 0.1 mV / second to 10 V / second. More preferably, it is in the range of 1 mV / second to 1 V / second, and more preferably in the range of 2 mV / second to 300 mV / second.

The time for the electropolymerization is not limited as long as an article having a metallic luster can be deposited, but it is preferably performed within the range of 1 second to 5 hours within the range of the applied voltage. More preferably, it is carried out within a range of 10 seconds to 1 hour.

The temperature of this electrolysis is not limited as long as an article having a metallic luster can be deposited by electrolytic polymerization, but it is preferably in the range of −20 ° C. or more and 60 ° C. or less.

この Moreover, this electrolysis is a reaction in which constituent substances in the atmosphere are rarely involved, and since it is carried out at a relatively low potential, it can be carried out in the atmosphere. From the viewpoint of avoiding the possibility of contaminating the formed film, such as oxidation of impurities in the electrolytic solution, it is preferable to carry out in an atmosphere of nitrogen gas or argon gas, but there is almost no fear of contamination. Nevertheless, in the case of forming electropolymerization, bubbling with an inert gas (nitrogen gas or argon gas) is also useful because there is a possibility that the electrode reaction may be affected if a large amount of oxygen is present in the solution. is there.

In this method, the thiophene polymer produced as described above is placed on an article and pressurized. As a result, an article having a metallic luster that is stably fixed on the article can be formed. Here, “pressurization” refers to applying pressure to the membrane, and so-called “rubbing” is also included in the pressurization of the membrane. Moreover, it is preferable that the thiophene polymer produced in this case is a powder. An image diagram relating to the manufacture of this article is shown in FIG.

Further, in this method, the article itself can be formed with only the thiophene polymer by placing the thiophene polymer prepared as described above in a mold made of metal or the like and pressurizing it. An image diagram relating to the manufacture of this article is shown in FIG.

Moreover, the range of the pressure at the time of pressurizing in this method is not particularly limited, but is preferably 10 kg / cm ² or more, and more preferably 50 kg / cm ² or more, for example. The upper limit is not limited as long as the film or article having metallic luster is not destroyed, but it is preferably in the range of 1.0 × 10 ⁵ kg / cm ² or less, more preferably 5. The range is 0 × 10 ⁴ kg / cm ² or less. The surface roughness can be reduced and glossiness can be better shown by setting it to 50 kg / cm ² or more, and the destruction of the structure of the article can be prevented by setting it to 5.0 × 10 ⁴ kg / cm ² or less. be able to.

In this method, it is also preferable to heat the article and the thiophene polymer when pressurizing. By doing so, there is an effect that the pressurization efficiency is further increased. Further, as described below, the toner particles can be dissolved and stably fixed to an article such as paper. The heating temperature is not particularly limited as long as it is not higher than the thermal decomposition temperature.

As described above, according to the present invention, it is possible to provide a method for producing an article having a novel metallic luster that does not use a solvent when forming an article having a metallic luster.

In the above-mentioned Patent Document 1, the inventors synthesized a deep blue polythiophene-based conductive polymer and dissolved it in a solvent to apply a coating solution on an article to form a gold-colored coating film. Have found to be. This is the world's first organic material that does not contain metals and dissolves in a solvent to give a gold-colored film. On the other hand, this time is based on the finding that a metal color tone is exhibited by applying pressure to this material. That is, the color change (chromism) based on a new principle that a deep blue powder exhibits a metallic color such as a gold color by pressure stimulation.

(Application example: Toner)
An application example of the thiophene polymer according to the present embodiment is wide and not limited as apparent from the above description, but an example considered to be very effective is a toner for metallic gloss color. That is, the metallic glossy color toner according to this application example described below is one in which a thiophene polymer is externally or internally added (or both types of addition) to binder resin particles, or does not contain a binder resin. The coalescence itself becomes the toner body.

As described above, the present toner is one in which the thiophene polymer is externally or internally added to the binder resin particles (or both addition modes), or the binder resin does not contain the thiophene polymer itself as the toner body. However, a component necessary as a toner may be included as long as the formation of an article having a metallic luster by the thiophene polymer is not hindered. Specifically, for example, a magnetic material such as iron powder, a wax, a charge control agent, an external additive, and the like can be included, but the invention is not limited thereto. An image diagram in this case is shown in FIG.

In the case of a toner in which a thiophene polymer is added externally or internally (or both of them) to the binder resin particles, the amount of the thiophene polymer to be included is limited as long as a metallic luster can be expressed. However, it is preferably 0.1% by weight or more, preferably 1% by weight or more based on the total amount of toner. Further, when no binder resin is used, the thiophene polymer occupies most of the weight of the toner.

Also, the printing method according to this application example is one in which a metallic gloss color toner containing a thiophene polymer is placed on an article, and the metallic gloss color toner is pressed to fix the toner. At this time, as described above, by applying heat simultaneously with pressurization, the toner binder and the like can be melted and fixed more easily on an article such as paper. FIG. 6 shows an image diagram of this process.

(Embodiment 2)
In the present embodiment, the so-called “rubbing” in which a film is formed by applying a force in the lateral direction among the pressurization referred to in the above embodiment will be described more specifically.

More specifically, the method according to this embodiment (hereinafter referred to as “the present method”) manufactures an article having a metallic luster by rubbing the thiophene polymer. In this method, “rubbing” (also referred to as “rubbing”) specifically means that a force is applied in a direction (lateral direction) different from the direction in which pressure is applied in a pressurized state, more specifically. This means that a thiophene polymer powder is placed on a substrate, and the pressure product is moved on the substrate in a state where the powder is pressurized by the pressure product. In this case, the pressurized material is not particularly limited, but for example, it is preferable that a weight is placed on the plate-like member itself or the plate-like member because a force can be applied uniformly. By doing in this way, the article | item provided with the metallic luster as mentioned above can be manufactured. Although this principle is still in the presumed range, it is thought that rubbing induces a regular arrangement with respect to the arrangement of the thiophene polymer, resulting in a film having a metallic luster.

Also, when rubbing in this method, the value of pressurization can be greatly reduced compared to the case of only pressurization. More specifically, a metallic (golden) gloss can be obtained by rubbing even at a pressure of 500 g / cm ² or less. In addition, the lower limit of pressurization may be a level that can be said to be pressurization, for example, 3 g / cm ² or more. That is, when rubbing, the pressure range is 3 g / cm ² or more and 500 g / cm ² or less, more preferably 300 g / cm ² or less.

As described above, according to the present embodiment, the pressure value can be further reduced, and a film having a metallic luster can be manufactured more easily.

(Example)
Here, the film | membrane concerning the said embodiment was produced actually and the effect was confirmed. This will be specifically described below.

In this example, when pressure was applied to the powder of 3-methoxythiophene (3MeOT) oligomer and compressed, it became a solid (tablet shape) with a golden tone. The pressure applied during tablet production was changed, and the appearance, specular reflection spectrum and arithmetic average roughness of each sample were evaluated.

(Production of 3MeOT oligomer)
An acetonitrile solution (10 mL) of iron (III) perchlorate (concentration 0.2 M) as an oxidizing agent is added to 10 mL of acetonitrile solution of 3 MeOT (concentration 0.1 M) as a raw material monomer, and polymerization is performed under a nitrogen atmosphere for 2 hours. Went. After the polymerization, the product, 3MeOT oligomer, was obtained through filtration, washing, and vacuum drying.

(Preparation of 3MeOT oligomer tablet)
Next, the 3MeOT oligomer obtained by the above method was ground and ground in a mortar for about 15 minutes, and then a tablet (diameter 13 mm) was produced using a tablet molding machine (Shimadzu Corporation Hand Press SSP-10A). . 100 mg of oligomer was used to make one tablet. Then, the weights applied to the case 50kg, 0.5t, 1t, 2t, 4t, 8t, 10t and changed (each as a pressure ^{^{0.038ton / cm 2, 0.38ton / cm}} 2, 0.75ton / cm 2 , 1.5 ton / cm ² , 3.0 ton / cm ² , 6.0 ton / cm ² , 7.5 ton / cm ² ), each of which was applied for 10 minutes to produce a plurality of tablets (50 kg sample was pressure For 1 minute). Then, the regular reflectance and surface roughness of the obtained tablet were measured.

(appearance)
The 3MeOT tablet produced by changing the pressure of the press was photographed with a digital microscope VHX-5000 manufactured by Keyence Corporation. The results are shown in FIGS. 7 to 13, respectively.

As a result, it was confirmed that samples prepared at any pressure exhibited a golden gloss. However, the sample with a weight of 1 t (the pressure was 0.75 ton / cm ² ) was broken when removed from the tablet press. Moreover, when the enlarged image of each sample was observed, it confirmed that an unevenness | corrugation was seen on the surface, so that the sample with a low pressure was observed.

(Specular reflection spectrum)
Next, the specular reflection spectrum of the sample prepared as described above was measured. For measurement of the reflection spectrum, MSV-370 spectrometer manufactured by JASCO Corporation was used. The specular reflection spectrum of each sample is shown in FIG.

As a result, the regular reflection spectrum of the tablet showed the same outline as that of the oligomer coating film. The maximum reflectivity increased as the pressure applied during pressing increased.

Therefore, a graph with the horizontal axis representing the pressure applied during pressing and the vertical axis representing the maximum reflectance is shown in FIG.

Further, the arithmetic average roughness Ra, which is a representative parameter of the surface roughness, was calculated for the manufactured article. For the calculation, a laser microscope VK-9700 manufactured by Keyence Corporation and its analysis software were used, and the average value of 10 line roughnesses per 500 μm fixed length was calculated. Regarding the measurement results, FIGS. 16 to 22 show a 3D image and arithmetic average roughness Ra by a laser microscope, and FIG. 23 shows a relationship between the pressure applied during pressing and Ra.

From this measurement result, it can be seen that the surface smoothness increases as the pressure applied during pressing increases. It can be seen that a sample having a large maximum reflectance of the tablet holds a relationship that Ra is small and surface smoothness is high.

As described above, it was confirmed that a metallic luster can be expressed by pressurization according to this example.

(Rubbing)
Further, 0.2 g of the prepared 3MeOT oligomer powder was sandwiched between two glass plates (0.5 cm × 7.6 cm × 5.2 cm), a 5 kg weight was placed on the glass plate, and this glass plate was reciprocated 50 times. It was. In this case, the pressure was 253 g / cm ² .

As a result, the powder which was black brown before rubbing (rubbing) became a gold-colored film after rubbing. This photograph is shown in FIG.

Also, a regular reflection spectrum was measured for this film. The result is shown by the solid line in FIG. As shown in this figure, a spectrum similar to that in the case of a coating film (a film obtained by dissolving 3MeOT oligomer powder in an organic solvent and then coating and drying on the substrate) (broken line) can be obtained, and the yellow color is strong. It was confirmed quantitatively that the film had a golden tone. The measurement conditions for this spectrum were an incident angle of 23 °, an aperture of 0.1 mm square, and the standard sample was a deposited aluminum film.

In addition, color measurement (L ^* a ^* b ^* ) was performed on this film. This result is shown in FIG.
Colorimetry uses a D65 light source and the results are expressed in the CIE LAB color system (L ^* a ^* b ^* ). In the figure, a ^* b ^* represents hue, redness increases when a * value becomes positive, greenishness increases when it becomes negative, yellowness increases when b ^* value becomes positive, and blueness increases when it becomes negative. Represents. For the measurement, a spectrocolorimeter CM-600d (Konica Minolta Co., Ltd.) was used, and data was visualized using color management software SpectraMagix NX (Konica Minolta Co., Ltd.). For comparison, the coating film is indicated by 〇, and the 3MeOT oligomer powder is indicated by ●.

As a result, the brightness and saturation of the non-glossy 3MeOT oligomer powder were small, whereas in the rubbing sample (▲) and coating film (◯), the brightness was significantly increased and the saturation was also in the first quadrant. It confirmed that it extended in the direction. Moreover, when the rubbing sample was compared with the coating film, it was confirmed that although the hue was almost the same, the saturation was slightly smaller. This is probably because the rubbing sample has a larger surface roughness than the coating film, and thus diffuse reflection is large, and as a result, the glossy yellow color is observed to fade.

Also, X-ray diffraction spectrum measurement was performed on this film. A diagram of the result is shown by the solid line in FIG. This measurement was performed by an out-of-plane method using a fully automatic horizontal multi-purpose X-ray diffractometer SmartLab (Rigaku). In the measurement by the out-of-plane method, information in the thickness direction of the layer can be obtained, and a peak is shown when there is a regular layer spacing in the thickness direction.

As a result, in the coating film of the dotted line, the (100) peak due to the edge-on lamella indicating gold (yellow except for gloss) is extremely large, and the (020) peak due to the face-on lamella indicating magenta (red purple) is small. It was confirmed that it was yellow when the gloss was removed. The interlayer distance of 1.13 nm from the (100) peak and the interlayer distance of 0.35 nm from the (020) peak were respectively calculated from the black equation. On the other hand, in the diffraction pattern of the broken-line oligomer powder, when the (100) peak and the (020) peak were compared, it was found that the edge-on lamella and the face-on lamella were the same or more. In this case, the color of the 3MeOT oligomer powder is a subtractive color mixture of yellow and magenta, which is brown, and is actually very dark brown, so it is close to black. Moreover, since the peak intensity is low in this powder, the number density of the lamella structure is extremely small, and it can be seen that there are many amorphous parts in the powder. On the other hand, in the rubbing sample, the (100) peak is remarkably increased compared to that, and since a sharp peak with a small half-value width is shown compared with the coating film, an edge-on lamella with a large crystal size is formed. (See FIG. 28). That is, rubbing has the effect of increasing the number density of edge-on lamellae and face-on lamellae contained in the powder sample, and it is considered that gold-colored gloss was developed especially by increasing the number density and size of edge-on lamellae.

As described above, it was confirmed that a metallic luster can be expressed by rubbing (rubbing) according to this example.

(Invention from another viewpoint)
By the way, the invention has been completed from another point of view regarding the development of metallic luster. This will be specifically described below.

However, the metal plating method has many limitations on the materials that can be surface treated. In addition, the surface technique uses a metal after all, and it is less expensive than the case where the entire article is used with a metal, but it becomes expensive. In particular, paints with the above metals added have metal particles that settle due to the difference in specific gravity between the polymer binder and the metal in the paint, making it easy to produce spots, and the metal is corroded and glossy. There are also problems such as loss and heavy coating.

Therefore, it is considered that the above problem can be solved if there is a substance that exhibits a metallic luster using a substance other than a metal. For example, there is a technique described in WO / 2014/021405. This non-metallic substance can be dissolved in a solvent, and can be uniformly applied to glass, plastic film, metal, and paper, and the coating film exhibits a golden or copper-colored gloss, and the gloss lasts for many years. The world's first substance.

However, the technique described in the above-mentioned patent document can form a film exhibiting metallic luster, but there is a problem in its strength.

Therefore, in view of the above problems, an object of the present invention is to provide an article and a toner having a metallic luster having high strength and a method for producing an article having a metallic luster.

An article having metallic luster according to an aspect of the present invention that solves the above problems is polyester resin, polycarbonate resin, polyvinylpyrrolidone resin, polystyrene resin, polymethyl methacrylate resin, and styrene acrylic copolymer resin, and thiophene. It has a metallic luster mixed with a polymer.

Although not limited in this respect, the weight of the thiophene polymer is preferably in the range of 0.1 to 99.9 when the weight of the article is 100.

In this respect, although not limited, the article is preferably a three-dimensional object.

A toner according to another aspect of the present invention includes a thiophene polymer mixed with at least one of a polyester resin, a polycarbonate resin, a polyvinyl pyrrolidone resin, a polystyrene resin, a polymethyl methacrylate resin, and a styrene acrylic copolymer resin. It has a metallic luster.

Further, although not limited in this aspect, the weight of the thiophene polymer is preferably in the range of 0.1 to 99.9 when the weight of the article is 100.

In addition, a method for manufacturing an article according to another aspect of the present invention includes a polyester resin, a polycarbonate resin, a polyvinyl pyrrolidone resin, a polystyrene resin, a polymethyl methacrylate resin, and a styrene acrylic copolymer resin and a thiophene polymer. , Having a metallic luster that is solidified by mixing with a solvent and removing the solvent.

In addition, a method for producing an article according to another aspect of the present invention includes a polyester resin, a polycarbonate resin, a polyvinyl pyrrolidone resin, a polystyrene resin, a polymethyl methacrylate resin, and a styrene acrylic copolymer resin, and a thiophene polymer. And a solvent for producing an article having a metallic luster.

Further, a three-dimensional object according to another aspect of the present invention is a polyester resin, a polycarbonate resin, a polyvinyl pyrrolidone resin, a polystyrene resin, a polymethyl methacrylate resin, and a styrene acrylic copolymer resin, a thiophene polymer, Are mixed.

In addition, the toner having metallic luster according to another aspect of the present invention includes a polyester resin, a polycarbonate resin, a polyvinylpyrrolidone resin, a polystyrene resin, a polymethyl methacrylate resin, and a styrene acrylic copolymer resin, and a thiophene polymer. The union is a mixture.

In addition, a method for producing a three-dimensional object having metallic luster according to another aspect of the present invention is a polyester resin, a polycarbonate resin, a polyvinyl pyrrolidone resin, a polystyrene resin, a polymethyl methacrylate resin, or a styrene acrylic copolymer resin. The heel thiophene polymer is mixed using a solvent and solidified by removing the solvent.

Further, a solution for producing an article having a metallic luster according to another aspect of the present invention includes a polyester resin, a polycarbonate resin, a polyvinylpyrrolidone resin, a polystyrene resin, a polymethyl methacrylate resin, and a styrene acrylic copolymer resin. It has at least one, a thiophene polymer, and a solvent.

As described above, according to the present invention, it is possible to provide an article and toner having a high-strength metallic luster and a method for producing an article having metallic luster.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention can be implemented in many different forms, and is not limited to specific examples of the embodiments and examples described below.

(Embodiment 3)
(Goods)
FIG. 29 is a schematic view of an article (hereinafter, also referred to as “this article”) 1 having a metallic luster according to the present embodiment. This article in this figure is a mixture of polyester resin, polycarbonate resin, polyvinyl pyrrolidone resin, polystyrene resin, polymethyl methacrylate resin and styrene acrylic copolymer resin, and thiophene polymer, Although this is an example in the form of a film in which an article is formed on a substrate, for example, a more three-dimensional and complicated shape shown in FIG. 30 is also possible.

(Polyester resin)
In this article, the polyester resin refers to a resin comprising a polycondensate of a polyvalent carboxylic acid and a polyhydric alcohol, and is not limited to this, but for example, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene. Examples include, but are not limited to, terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycyclohexanedimethyl terephthalate, polytrimethylene naphthalate, polycyclohexanedimethylene terephthalate, polytritetramethylene naphthalate, and mixtures thereof. .

In the present article, the average molecular weight of the polyester resin is not limited as long as it has a metallic luster, but is preferably 1000 or more and 1000000 or less, more preferably 3000 or more and 100000 or less.

(Polycarbonate resin)
In the present article, the polycarbonate resin is a resin having a carbonate group as a constituent element, and can be produced by, for example, bisphenol A and phosgene. Moreover, in this article, the average molecular weight of the polycarbonate resin is not limited as long as it has a metallic luster, but it is preferably 1000 or more and 1000000 or less, more preferably 3000 or more and 100000 or less.

(Polyvinylpyrrolidone (PVP) resin)
In the present article, the polyvinyl pyrrolidone resin refers to a resin obtained by polymerizing N-vinyl-2-pyrrolidone. Moreover, in this article, the average molecular weight of the polyvinylpyrrolidone resin is not limited as long as it has a metallic luster, but it is preferably 1,000 or more and 1,000,000 or less, more preferably 3000 or more and 100,000 or less.

(Polystyrene resin)
In this article, the polystyrene resin refers to a resin obtained by polymerizing styrene. In this article, the average molecular weight of the polystyrene resin is not limited as long as it has a metallic luster, but it is preferably 1000 or more and 1000000 or less, more preferably 3000 or more and 500000 or less, and more preferably Is 300,000 or less.

(Polymethyl methacrylate resin (acrylic resin))
In this article, polymethyl methacrylate (PMMA) resin refers to a resin obtained by polymerizing an acrylate ester. The average molecular weight of the polymethyl methacrylate resin is not limited as long as it has a metallic luster, but is preferably 1000 or more and 1000000 or less, more preferably 3000 or more and 500000 or less.

(Styrene acrylic copolymer resin)
In the present article, the styrene acrylic copolymer resin refers to a copolymer compound of acrylonitrile and styrene. The average molecular weight of the styrene acrylic copolymer resin is not limited as long as it has a metallic luster, but it is preferably 1000 or more and 1000000 or less, more preferably 3000 or more and 500000 or less.
(Thiophene polymer)
In the present article, the “thiophene polymer” refers to a polymer in which two or more thiophenes are bonded to each other and refers to a compound represented by the following general formula.

In the above formula, R is a substituent and is not limited as long as it can impart a metallic luster to the film, but is not limited to an alkoxy group, an amino group, an alkyl group, a hydroxyl group, a hydroxyalkyl group, an aryl group, a cyano group, Or it is preferable that it is either halogen. R may be one or two per thiophene ring. Moreover, in the thiophene polymer according to the present embodiment, the Rs of the thiophenes may be the same or different. Furthermore, when the thiophene polymer is doped with anions, it exhibits a gold color and copper color similar to gold and copper. Anions include perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, chloride ion, bromide ion, sulfate ion, acetate ion, nitrate ion, citrate ion, oxalate ion, p-toluenesulfonic acid Ion, polystyrene sulfonate ion and the like.

In the above formula, when R is an alkoxy group, it is not limited, but the number of carbon atoms is preferably 1 or more and 8 or less, more specifically, 3-methoxythiophene, 3,4-dimethoxy. Thiophene, 3-ethoxythiophene, 3-propoxythiophene, 3-butoxythiophene, 3-methoxy-4-methylthiophene, 3-ethoxy-4-methylthiophene, 3-butoxy-4-methylthiophene, 3,4-diethoxy Examples thereof include thiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene, and the like.

In the present article, the molecular weight of the “thiophene polymer” is not limited as long as it can have a metallic luster and can be formed as a film, but the weight required by the GPC measurement method. The average molecular weight distribution peak is preferably in the range of 200 to 30,000, more preferably in the range of 500 to 10,000.

In the present article, the weight of the thiophene polymer is preferably in the range of 0.1 to 99.9, more preferably 0.5 to 99, when the total weight of the article is 100. Range.

In the present article, the thiophene polymer is not limited as long as it can be produced, and various methods can be adopted. For example, thiophene polymers can be made by chemical polymerization or electrolytic polymerization.

(Chemical polymerization)
Here, the “chemical polymerization method” refers to polymerization performed in at least one of a liquid phase and a solid phase using an oxidizing agent.

Specifically, in this method, (1) a step of polymerizing thiophene using an oxidizing agent to obtain a solution containing a thiophene polymer, (2) removing unreacted raw materials and by-products from the solution containing the thiophene polymer. And obtaining a thiophene polymer powder.

First, in this method, (1) thiophene is polymerized using an oxidizing agent to prepare a solution containing this thiophene polymer. The “thiophene” used here and the resulting “thiophene polymer” are those described above. As described above, the thiophene polymer is preferably in the range of a so-called oligomer, and specifically, the polymerization is preferably performed so that the distribution peak of the weight average molecular weight is in the range of 200 to 30000.

In this step, the oxidizing agent is not limited as long as the thiophene polymer can be produced, and various ones can be used. For example, ferric salt, cupric salt, cerium salt, dichromic acid Examples thereof include salts, permanganate, ammonium persulfate, boron trifluoride, bromate, hydrogen peroxide, chlorine, bromine and iodine. Among them, ferric salt is preferable. Hydrates may also be used. In this case, the pair of ions can be appropriately adjusted and is not limited. For example, chloride ion, bromide ion, citrate ion, oxalate ion, paratoluenesulfonate ion, perchloric acid. Ion, hexafluorophosphate ion, tetrafluoroborate ion, etc., among which perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, chloride ion, bromide ion, and para Use of at least one of toluene sulfonate ions is preferable because a metallic luster close to a golden color defined by numerical evaluation by a colorimeter can be obtained. The reason why a metallic luster close to gold can be obtained is speculated, but perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, chloride ion, bromide ion, paratoluenesulfonate ion During polymerization, it is incorporated into the thiophene polymer as a dopant, and is bound and stabilized by the cation moiety generated in the thiophene polymer, which contributes to the formation of an ordered molecular orientation structure (formation of lamellar crystal structure). It is done. In fact, when films having metallic luster are analyzed, it has been confirmed that they exist stably.

In this method, the thiophene polymer produced as described above is preferably prepared as a powdered thiophene polymer (thiophene polymer powder) by removing the solvent. By doing so, it is possible to produce an article having metallic luster by mixing with a polyester resin while being dissolved in a solvent described later. In addition, when an oxidizing agent containing the perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, chloride ion, bromide ion, or paratoluenesulfonate ion is used, the polymer is stably used. Since it is bonded, the remaining metal gloss can be stably maintained.

(Electropolymerization)
In the present article, as described above, the thiophene polymer can also be produced using electrolytic polymerization. In the present embodiment, electrolytic polymerization refers to a solution-insoluble polymer film on a conductor by dissolving a substance (monomer) serving as a polymer precursor in a solution containing a supporting electrolyte, and then subjecting the monomer to electrode oxidation. Is a method of forming

The solvent of the solution used in this embodiment is not particularly limited. For example, in addition to water and alcohol, Akira Fujishima, Masuo Aizawa, Toru Inoue, Electrochemical Measurement, Gihodo Publishing, Vol. 107-114 Page, 1984 can be used. A mixed solvent of various solvents is also preferable. Furthermore, using an anionic surfactant such as sodium dodecyl sulfate, a cationic surfactant such as dodecyltrimethylammonium bromide, and a nonionic surfactant such as polyoxyethylene lauryl ether, numerical evaluation using a colorimeter The metallic luster close | similar to gold | metal | money prescribed | regulated by (1) can be obtained and it is preferable.

Further, the supporting electrolyte of the solution used in the present embodiment is an essential component in electrolysis, and preferably has a cation or an anion that is sufficiently dissolved in a solvent and hardly electrolyzed, and is not limited thereto. However, it is preferable to use at least one of lithium salt, sodium salt, potassium salt, calcium salt, and tetraalkylammonium salt if attention is paid to cations, and halide, sulfate, nitrate, phosphoric acid, etc. if attention is paid to anions. It is preferable to use at least one of a salt, a perchlorate, a tetrafluoroborate, and a hexafluorophosphate. The concentration of the supporting electrolyte is not limited, but is preferably 0.001M or more and solubility or less, and more preferably 0.01M or more and 5M or less.

In this embodiment, the concentration of the thiophene monomer used in the electropolymerization in the electrolytic solution is not limited, but is preferably 0.1 mM or more and less than or equal to the solubility, more specifically 0.5 mM. More preferably, it is 1 M or less.

The conductor as the working electrode is not limited as long as it is a substance that is stable against electrode oxidation in both the three-electrode type and the two-electrode type. For example, as described above, A transparent glass electrode coated with indium tin (hereinafter abbreviated as “ITO”) or tin oxide, a metal electrode, an alloy electrode such as stainless steel, a glassy carbon electrode, or the like can be suitably used. Moreover, as a counter electrode, in addition to the electrode material, a metal electrode such as stainless steel or a copper plate can be suitably used. The reference electrode is not limited, but for example, a silver / silver chloride electrode (Ag / AgCl electrode) or a saturated calomel electrode can be preferably used.

この Moreover, this electrolysis is a reaction in which constituent substances in the atmosphere are rarely involved, and since it is carried out at a relatively low potential, it can be carried out in the atmosphere. From the viewpoint of avoiding the possibility of contaminating the formed film, such as oxidation of dissolved oxygen in the electrolytic solution, it is preferably performed in a nitrogen gas or argon gas atmosphere, but there is little concern about contamination. Nevertheless, in the case of forming electropolymerization, bubbling with an inert gas (nitrogen gas or argon gas) is also useful because there is a possibility that the electrode reaction may be affected if a large amount of oxygen is present in the solution. is there.

(Production method)
This article is a mixture of the thiophene polymer synthesized by the above chemical polymerization or electrolytic polymerization and at least one of polyester resin, polycarbonate resin, polyvinyl pyrrolidone resin, polystyrene resin, polymethyl methacrylate resin and styrene acrylic copolymer resin. In this mixing, it is preferable to use a solvent. The solvent is not limited as long as the thiophene polymer can be mixed with at least one of the polyester resin, polycarbonate resin, polyvinyl pyrrolidone resin, polystyrene resin, polymethyl methacrylate resin and styrene acrylic copolymer resin. For example, nitromethane, γ-butyrolactone, acetonitrile, propylene carbonate, dimethyl sulfoxide, N-methyl-2-pyrrolidone and a mixture thereof can be used, but are not limited thereto.

The ratio of the thiophene polymer to the ratio of at least one of polyester resin, polycarbonate resin, polyvinyl pyrrolidone resin, polystyrene resin, polymethyl methacrylate resin and styrene acrylic copolymer resin may be in the above range, but the concentration of the solvent and this mixture The ratio of is not limited as long as it can be dissolved and can be appropriately adjusted as long as the necessary viscosity can be obtained. For example, when the total weight of the polyester resin and the thiophene polymer is 1, It is preferably 0.1 or more and 500 or less.

And after apply | coating the produced solution on a board etc. and forming in a desired shape, it can be dried and the article which maintained the desired three-dimensional shape can be formed by removing a solvent. Of course, the three-dimensional shape includes a film, and the strength of the film has a very high strength, as will be apparent from Examples described later.

As described above, in this article, even when a thiophene polymer is mixed with at least one of a polyester resin, a polycarbonate resin, a polyvinyl pyrrolidone resin, a polystyrene resin, a polymethyl methacrylate resin, and a styrene acrylic copolymer resin, the metallic luster is not lost. An article with higher strength can be provided.

In this article, the reason why the thiophene polymer exhibits a metallic luster is in the range of speculation, but it is considered that the molecules constituting the thiophene polymer are regularly oriented and reflect a specific wavelength. This is supported by the fact that the prepared film containing the thiophene polymer shows a sharp peak in X-ray diffraction.

However, considering the above background, it is generally considered that when a thiophene polymer is mixed with a resin that is another mixture, the above-mentioned special regular arrangement is disturbed and a structure exhibiting metallic luster cannot be realized. It is done. However, in this article, polyester resin, polycarbonate resin, polyvinyl pyrrolidone resin, polystyrene resin, polymethyl methacrylate resin, and styrene-acrylic copolymer resin are used, among other resins. It has been found that even when at least one of a resin, a polyvinyl pyrrolidone resin, a polystyrene resin, a polymethyl methacrylate resin and a styrene acrylic copolymer resin enters, the metallic luster is not lost. In addition, at least one of polyester resin, polycarbonate resin, polyvinyl pyrrolidone resin, polystyrene resin, polymethyl methacrylate resin and styrene acrylic copolymer resin can be appropriately adjusted in molecular weight, and by adjusting the solvent to be mixed, It is possible to adjust the viscosity of the solution.

(toner)
By the way, the article according to the present embodiment is a mixture of a thiophene polymer and at least one of a polyester resin, a polycarbonate resin, a polyvinyl pyrrolidone resin, a polystyrene resin, a polymethyl methacrylate resin, and a styrene acrylic copolymer resin. . The polyester resin itself is used as a binder for toner used in, for example, printers and copiers, and this article can be used as toner for printers and the like. When the toner is used, it can be realized by making the mixture of the polyester resin and the thiophene polymer into fine particles. As a method for making fine particles, an article in which the polyester resin and the thiophene polymer are mixed can be crushed to obtain a desired particle size. For example, the viscosity of the prepared solution is lowered, and an inkjet nozzle is used. A droplet having a size slightly larger than the desired particle size is formed by spraying used, and the solvent can be removed from the droplet to obtain a dried particle. Of course, other resins, polycarbonate resins, polyvinyl pyrrolidone resins, polystyrene resins, polymethyl methacrylate resins, styrene acrylic copolymer resins, and the like can be used as long as possible.

As described above, according to this embodiment, an article having a higher metallic luster can be obtained.

(Example)
Here, the product according to the above embodiment was actually manufactured to confirm the effect. This will be specifically described below.

(Thiophene polymer)
First, a monomer of 3-methoxythiophene (hereinafter referred to as “3MeOT”) was distilled before polymerization to remove impurities. 5.418 g of the distilled monomer was stirred with a propeller stirrer for 30 minutes while bubbling nitrogen into 475 ml of acetonitrile to prepare a monomer solution of 0.1 mol / l.

Next, 48.02 g of iron (III) perchlorate.n hydrate (Fe (ClO ₄ ) ₃ .nH ₂ O) as an oxidant is added to 475 ml of acetonitrile, and dissolved by ultrasonic dispersion for 20 minutes. Then, an oxidizing agent solution 0.2 mol / l was prepared.

Then, the monomer solution was put into the polymerization cell, and the oxidant solution was slowly dropped with a burette and polymerized for 2 hours. By this operation, a 3MeOT oligomer exhibiting a deep blue color was obtained.

And the solution containing 3MeOT oligomer after superposition | polymerization was put into the glass filter, and suction filtration was carried out. The residue remaining on the filter of the glass filter was washed with methanol and suction filtration was repeated.

Thereafter, the residue after washing was put in a vacuum dryer and vacuum-dried at 50 ° C. for 90 minutes to dry the oligomer.

(Mixture of thiophene polymer and polyester resin)
The prepared oligomers, polyester (PES) resin (Toyobo Co., Ltd., Byron 200, average molecular weight 17,000), and nitromethane and γ-butyrolactone (hereinafter referred to as GBL) as solvents are shown in Table 1 below. The amounts shown in Table 2 were mixed and stirred. In the following table, 3MeOT: PES represents the weight ratio of the oligomer and the polyester, and hereinafter the notation is referred to as a sample name. Therefore, 1: 0 represents an oligomer-only solution containing no resin.

(Manufacture of goods)
The solution was dropped onto a well-washed glass substrate with a dropper. The coating film of nitromethane solvent was dried at room temperature for 1 hour (20 ° C., 40% RH), and the coating film of GBL solvent was dried for 30 minutes (45 ° C.) with a constant temperature hot air dryer.

FIG. 31 shows a film prepared from the nitromethane solution shown in Table 1 above. The ratio in the figure is the mass ratio of 3MeOT: PES. 1: 0 is an oligomer-only film that does not contain PES.

FIG. 32 shows a film prepared from the GBL solution shown in Table 2 above. The ratio in the figure is the mass ratio of 3MeOT: PES. 1: 0 is an oligomer-only film that does not contain PES.

(Specular reflection spectrum)
Here, in FIGS. 33 and 34, the specular reflection spectra of the coating films prepared from the solutions in Tables 1 and 2 above were measured with a micro-ultraviolet-visible-near infrared spectrophotometer (MSV-370, manufactured by JASCO Corporation). The results are shown. The wavelength interval was 0.5 nm, and the aperture size was 100 × 100 μm.

According to the specular reflection spectrum of the coating film prepared from the nitromethane solution shown in FIG. 33, it was confirmed that the coating film showed a slight decrease in reflectance due to the addition of the polymer resin, but no rising wavelength shift was observed.

Further, it was confirmed that the coating film prepared from the GBL solution shown in FIG. 34 had improved reflectance by the addition of the polymer resin. In addition, since the rising wavelength is shifted by a short wavelength by the addition of the polymer resin, it was found that the color can be changed by the addition of the resin.

(Colorimetric data)
The results of film color measurement using a spectrocolorimeter (CM-600d manufactured by Konica Minolta) are shown in Tables 3 and 4 below. In this case, color measurement was performed with the result that the light source was D65, the viewing angle was 10 degrees, and the specular reflection was included.

35 and ^{^{36, CIE1976 (L *, a *}} , b *) L in the color space (http://www.konicaminolta.jp/instruments/knowledge/color/part1/07.html) ^{*, a *,} The values of b ^* are plotted respectively.

Tables 5 and 6 show values compared with gold films prepared by vacuum deposition. ΔE * ab represents a color difference (a distance in the color space). In addition, FIGS. 37 and 38 show the difference between the coating film and the gold deposition film in the case of the nitromethane solution and the GBL solution. FIGS. 39 and 40 show the coating film and the gold deposition in the case of the nitromethane solution and the GBL solution, respectively. The color difference ΔE * ab from the film will be described.

(Measuring mechanical strength)
Next, the mechanical properties of the coating film were evaluated based on the scratch hardness (JIS 5600-5-4). As the pencil, Mitsubishi Pencil High Uni was used, and the hardness of the hardest pencil with no scratch marks on the coating film is shown in Table 7 and Table 8, respectively.

As a result, the coating strength was improved by increasing the amount of polymer resin added.

As described above, when a coating liquid in which a polyester resin is mixed with 3-methoxythiophene oligomer exhibiting a metallic luster is prepared and coated on a substrate, a metallic luster film having excellent mechanical strength without losing the golden luster is obtained. We were able to make it.

(Production of three-dimensional shape)
Note that by adjusting the viscosity of the prepared solution, a three-dimensional article can be created instead of a film. FIG. 41 shows a photograph of an example of an article having an actual three-dimensional shape instead of a film. As shown in the figure, a three-dimensional article having high strength can be obtained.

(Combination with other resins: Preparation of mixed coating solution of thiophene polymer and resin)
As in the case of the above PES, a combination with another resin was performed to prepare a coating solution. Specifically, 10 mg of various resins shown in Table 9 below are completely dissolved in 1.0 g of γ-butyllactone (hereinafter referred to as “GBL”) or 1.0 g of nitromethane, and the thiophene polymer prepared above is dissolved in the solution. 10 mg was mixed and stirred.

(Combination with other resins: creation of membranes)
Then, the prepared coating solution was dropped onto a well-washed glass substrate with a dropper and applied, and the coating film was dried with a constant temperature hot air dryer for 1 hour (60 ° C.). In all cases, the film thickness was about 18 μm.

FIG. 42 shows a photograph of the prepared coating film and a coating film not containing resin as a comparative example. In the figure, from the upper left, a coating film not containing a resin (nitromethane solvent) as a comparative example, a coating film not containing a resin (GBL solvent), PES-N, and PES-G as comparative examples are shown. , PVP, PS, PMMA, and StAc, respectively. For PS, PMMA, and StAc, since the back side of the film developed a gold color, it was taken as a photograph of the back side.

(Combination with other resins: reflection spectrum)
43 to 45, reflection spectra were measured using a spectrocolorimeter (CM-600d manufactured by Konica Minolta). The light source was D65, the viewing angle was 10 degrees, and the measurement was performed by a measurement method including antireflection (SCI method). FIG. 43 shows total reflection spectra of a film not containing a resin and a PEN-N film prepared from a nitromethane solvent, and FIG. 44 is a film not containing a resin and a PES-G film, a PC film and a PVP prepared from a GBL solvent. 45 shows the total reflection spectrum of the film, and FIG. 45 shows the total reflection spectrum of the film not containing the resin made from the GBL solvent, the PES film, the PMMA film, and the StAc film, respectively.

(Spectral colorimetry)
Next, using the above-described spectrocolorimeter, color measurement was performed on the gold-colored surface of the film shown in the above figure. The light source was D65, the viewing angle was 10 degrees, and the measurement was performed by a measuring method (SCI method) including antireflection light. ^{Incidentally,} L ^*, a *, ^{b *} ^{^{values, CIE1976 (L *, a *}} , b) the lightness ^{L *} in the color space, the hue and saturation ^a *, represents the ^{b *,} JISZ8781-4: 2013 standard Based on. The absolute value data of the colorimetry obtained as a result is shown in Table 10 below, and graphs of L ^* , a ^* , b ^* of the values are shown in FIGS. In FIG. 46, ● represents a gold vapor-deposited film, ■ 1 represents a gold-colored film containing no resin prepared from a nitromethane solvent, and ■ 2 represents a PES-N film. In FIG. 47, ● represents a gold vapor deposition film, ■ 1 represents a gold-tone film not containing a resin prepared from a GBL solvent, ■ 2 represents a PES-G film, 3 represents a PC film, and 4 represents a PVP. Each membrane is shown. In FIG. 48, ● represents a gold deposited film, ■ 1 represents a gold-colored film containing no resin prepared from a GBL solvent, ■ 2 represents a PS film, ■ 3 represents a PMMA film, and ■ 4 represents a StAc film. ing.

Next, in order to compare the color of the gold-colored film obtained here and the vapor-deposited metal gold, the color difference ΔE ^* ab based on the colorimetric value of the gold vapor-deposited film and L ^* , a The values ΔL ^* , Δa ^* and Δb ^* between the values of ^* and b ^* are shown in Table 11 below, and the results plotted in FIGS. 49 to 51 are shown. However, the color difference ΔE ^* ab is a linear distance from the reference color (gold vapor deposition film) in the L ^* a ^* b ^* space, and is given by the following equation. 49 shows the color difference from the gold vapor deposition film. In the figure, ● represents a gold vapor deposition film, ■ 1 represents a gold-tone film not containing a resin prepared from a nitromethane solvent, and ■ 2 represents a PES-N film. ing. FIG. 50 also shows the color difference from the gold vapor deposition film. In the figure, ● represents a gold vapor deposition film, ■ 1 represents a gold-tone film not containing a resin prepared from a GBL solvent, and ■ 2 represents a PES-G film. , ■ 3 indicates a PC film, and ■ 4 indicates a PVP film. In FIG. 51, ● indicates a gold deposited film, ■ 1 indicates a gold-colored film containing no resin prepared from a GBL solvent, ■ 2 indicates a PS film, ■ 3 indicates a PMMA film, and ■ 4 indicates a StAc film. ing.

Next, a comparison was made with a film containing no resin. Specifically, in order to compare the color of the film obtained above and the film containing no resin, the color difference ΔE ^* ab and L The differences ΔL ^* , Δa ^* , Δb ^* between the values of ^* , a ^* , b ^* are shown in Table 12 below, and the results plotted in FIGS. 52 to 54 are shown. 52 shows the color difference from the gold vapor deposition film. In the figure, ● represents a gold vapor deposition film, ■ 1 represents a gold-tone film not containing a resin prepared from a nitromethane solvent, and ■ 2 represents a PES-N film. ing. 53 also shows the color difference from the gold vapor deposition film. In the figure, ● represents a gold vapor deposition film, ■ 1 represents a gold-colored film not containing a resin prepared from a GBL solvent, and ■ 2 represents a PES-G film. , ■ 3 indicates a PC film, and ■ 4 indicates a PVP film. In FIG. 54, ● indicates a gold deposited film, ■ 1 indicates a gold-colored film containing no resin prepared from a GBL solvent, ■ 2 indicates a PS film, ■ 3 indicates a PMMA film, and ■ 4 indicates a StAc film. ing.

(Gold film formation when the amount of resin added is changed)
Next, in the coating film when the amount of the resin added was increased by 8 times or more relative to the oligomer, it was confirmed that the same golden tone gloss was exhibited. The results are shown below.

(Production)
The thiophene polymer was performed in the same manner as in the above example. Also, 80 mg of various resins shown in Table 13 below were completely dissolved in 1.0 g of GBL, and 10 mg of the prepared 3MeOT oligomer was mixed with the solution and stirred. Next, the solution was dropped onto a well-washed glass substrate with a dropper and applied, and the coating film was dried with a constant temperature hot air dryer for 1 hour (60 ° C.). The film thickness was about 50 μm.

Here, FIG. 55 shows a photograph of the film prepared above and a film not containing resin (dried at 60 ° C.). However, PS, PMMA, and StAc are images of the bonding surface (back surface) with the glass substrate.

(Specular reflection spectrum)
FIG. 56 shows a specular reflection spectrum of the surface of PES and the adhesive surface (back surface) of PS, PMMA, and StAc among the prepared coating films. The results measured with MSV-370) manufactured by the company are respectively shown. Comparing the results shown in this figure with the same results as described above, there was no difference in the rising wavelength and the reflectance, so that it was confirmed that even when the resin was excessively mixed with the oligomer, golden gloss was developed.

(Spectral colorimetry)
Next, the values of L ^* , a ^* , and b ^* of each film are shown in Table 14 below, and a graph of L ^* and a ^* -b ^* of the values is shown in FIG. As a result, all of the resin films have values close to those of gold vapor deposition, but the values of a ^* and b ^* are slightly lower than those of the gold vapor deposition film, indicating that green and blue are slightly strong. In comparison with the above table, there was not much change in color tone even when the amount of resin was increased. In the figure, ● is a gold vapor deposition film, ■ 1 is a gold-tone film not containing a resin made from GBL solvent, ■ 2 is a PES film, ■ 3 is a PS film, ■ 4 is a PMMA film, ■ Reference numeral 5 denotes a StAc film.

Next, in order to compare the color of the gold-colored film and the vapor-deposited metal gold, the color differences ΔL ^* , Δa ^* , Δb ^* with reference to the colorimetric values of the gold vapor-deposited film are shown in Table 15 below. The results plotted are shown in FIG. In this figure, ● is a gold vapor deposition film, ■ 1 is a gold-tone film not containing a resin made from GBL solvent, ■ 2 is a PES film, ■ 3 is a PS film, ■ 4 is a PMMA film, (5) indicates a StAc film, respectively.

Next, in order to compare the colors of the gold-colored film and the film containing no resin, the color differences ΔL ^* , Δa ^* , Δb ^* with reference to the colorimetric values of the gold deposited film are shown in the following table. FIG. 59 shows the results plotted in FIG. In this figure, ● is a gold vapor deposition film, ■ 1 is a gold-tone film not containing a resin made from GBL solvent, ■ 2 is a PES film, ■ 3 is a PS film, ■ 4 is a PMMA film, (5) indicates a StAc film, respectively.

(X-ray diffraction spectrum)
Here, X-ray diffraction analysis was performed on the surface of the PES film in which the golden luster was developed and the back surface of the PMMA film, and knowledge about the presence or absence of the crystalline structure (lamella structure) attributed to the thiophene polymer was obtained. The measurement was performed by the thin film method using SmartLab manufactured by Rigaku Corporation. In this case, the film thickness was about 50 μm.

FIG. 60 shows these XRD patterns. In any pattern, a sharp peak was confirmed around 7.79 degrees, and lamella crystals were present in the film, producing a lamellar correlation distance of 1.13 nm.

(X-ray photoelectron spectroscopy (XPS))
By X-ray high electron spectroscopy analysis, knowledge on the constituent elements and abundance of the film surface (surface up to a depth of about 2.5 nm) was obtained. For the measurement, Quantera II manufactured by PHI was used, and the X-ray source was monochromatic Al (1486.6 eV).

Fig. 60 shows the wide scan spectrum. According to this, only peaks of oxygen O, carbon C, chlorine Cl, and sulfur S were confirmed in both PES and PMMA.

Further, narrow scan spectra in the vicinity of S2p and Cl2p are shown in FIGS. Signals of sulfur derived from thiophene ring and chlorine derived from dopant perchloric acid were clearly observed within 2.5 nm in depth on both PES surface and PMMA surface exhibiting golden luster. That is, it was found that a thiophene polymer was present on the outermost surface and the rearmost surface of a 50 μm-thick film, and it was found that a golden tone was developed by lamellar crystals formed by the thiophene polymer. The chlorine and sulfur atom number concentrations obtained from the obtained spectrum are shown in Table 17 below. From this concentration, it was found that the thiophene polymer obtained in this example was doped with about 3 chloride ions per 10 units of the thiophene ring.

The present invention has industrial applicability as an article having a metallic luster and a method for producing the same.

Claims

A method for producing an article having a metallic luster by pressurizing a thiophene polymer.
The method for producing an article with metallic luster according to claim 1, wherein the thiophene polymer is formed by chemical polymerization or electrolytic polymerization.
Metal gloss color toner containing thiophene polymer.
A printing method in which a metallic glossy color toner containing a thiophene polymer is placed on an article, and the metallic glossy color toner is pressed and fixed.
The method for producing an article with metallic luster according to claim 1, wherein the thiophene polymer is rubbed.