JPWO2009028393A1 - Fluorescent color developing polyvinyl alcohol-based resin molding and method for producing the same - Google Patents

Abstract

A PVA molded article containing 0.5% by mass or more of phosphor fine particles having an average particle diameter of 50 nm or less that emits fluorescence in the wavelength range of 350 to 700 nm under ultraviolet irradiation, and (i) the PVA molded article under ultraviolet irradiation The metal ion (A) that forms the metal compound (F) that fluoresces in the wavelength range, or is immersed in a liquid containing the metal ion (A) and the activator ion (C); and (ii) the metal ion A metal that emits fluorescence in the wavelength range in a PVA molded body by immersing in a solution containing ions (B) that react with (A) to form a metal compound (F) that emits fluorescence in the wavelength range under ultraviolet irradiation. After producing phosphor fine particles having an average particle diameter of 50 nm or less made of the compound (F), (iii) the PVA compact is further transformed into a liquid containing metal ions (A) and ions (B) or metal ions (A ), Ions (B), and activator ions (C), so that they exist under visible light. Not certified, to produce a PVA-based resin molded article containing the fluorescent fine particles of nm size emits strong fluorescence under ultraviolet irradiation.

Description

  The present invention relates to a fluorescent color-developing polyvinyl alcohol-based resin molded body containing ultrafine phosphor particles in a molded body and a method for smoothly producing the molded body. More specifically, the present invention does not visually recognize the presence of phosphor fine particles under visible light, emits clear fluorescence under ultraviolet irradiation, has high ultraviolet absorption performance, and is a gas such as oxygen. The present invention relates to a fluorescent color-forming polyvinyl alcohol-based resin molding in which ultrafine particles of fluorescent particles that change in fluorescence coloring property due to surface adsorption of the particles are dispersed therein and a method for producing the same. The fluorescent coloring polyvinyl alcohol-based resin molded article of the present invention makes use of the above-described properties to prevent counterfeiting in banknotes, securities, confidential documents, ID cards, product tags, etc., wallpaper, carpets, clothing, glass interlayers and glass pasting. It can be effectively used for applications such as a film that combines ultraviolet shielding and decoration, such as a film for film deposition, and a sensing material that utilizes gas surface adsorption.

Fluorescent substances that emit fluorescence when irradiated with ultraviolet rays have been used for anti-counterfeiting measures and decorative materials. Phosphors that emit fluorescence when irradiated with ultraviolet light do not emit light when exposed to visible light, such as indoors where sunlight or ordinary lighting equipment is installed, but fluoresce when irradiated with ultraviolet light in the dark. By irradiating ultraviolet rays, characters, figures, patterns, shapes, etc. can be raised and visually recognized.
Synthetic resin moldings for decoration or anti-counterfeiting using phosphors include synthetic fibers in which phosphor particles that emit fluorescence under ultraviolet irradiation are attached to the surface, phosphor particles that emit fluorescence under ultraviolet irradiation Known are phosphor-containing synthetic fibers produced by melt spinning, wet spinning, dry spinning, etc. using a resin composition or resin solution to which is added, and fabrics and papers formed using the synthetic fibers ( (See Patent Documents 1 to 4).

However, the fibers with phosphor particles attached to the surface generally have unevenness on the fiber surface because the phosphor particles with a large particle size of micron order are attached to the fiber surface, and the fiber surface is liable to be poor. The phosphor particles adhering to the fiber easily fall off from the fiber surface due to external stress such as friction and bending.
In addition, when spinning by melt spinning, wet spinning, dry spinning, etc. using a resin composition or resin solution to which phosphor particles are added, the phosphor particles usually have a large particle size on the order of microns, During spinning, the filter and spinning nozzle of the spinning device are clogged, and the resulting yarn breakage during the spinning process is likely to occur, and the process passability during fiber production tends to be poor.

In addition, in the above-described conventional techniques, as described above, phosphor particles of the micron order are used, and therefore, visible particles having a long wavelength are formed by the phosphor particles attached to the fiber surface or contained in the fiber. Light diffraction or scattering occurs, and the presence of phosphor particles is visually recognized even under visible light, which tends to be unsuitable for applications such as forgery prevention.
If the particle size of the phosphor particles to be contained in the fiber or other synthetic resin molding can be reduced to phosphor particles of 50 nm or less, which is 1/10 or less of the wavelength of visible light, visible light from the phosphor particles. Therefore, the problem that the presence of phosphor fine particles contained in the molded body is visually recognized under visible light can be prevented.
However, the phosphor particles are present in the compact at a nanometer order particle size, especially a particle size of 50 nm or less, and at a high concentration that emits strong fluorescence that is clearly and easily visible when irradiated with ultraviolet rays. The synthetic resin molded body made and the manufacturing method thereof have not been known so far.

Japanese Patent Laid-Open No. 9-67674 JP 11-93096 A JP-A-6-128807 JP 2000-290831 A “J. Am. Chem. Soc.”, 1986, Vol. 8, p3358-3361 “Coloring Materials”, 1958, Vol. 31, P85 “Science”, 2000, Vol. 290. , P314-317

The object of the present invention is to make fluorescent particles having an average particle diameter of 50 nm or less that emits strong fluorescence that is clearly and easily visible when irradiated with ultraviolet rays, while the presence of fluorescent fine particles is not visible under visible light. An object of the present invention is to provide a fluorescent color-forming synthetic resin molded body in which body fine particles are contained in a dispersed state in a synthetic resin molded body.
Furthermore, the present invention contains phosphor fine particles having a particle size of 50 nm or less in average particle size with high visible light transmittance and excellent transparency, while having low ultraviolet light transmittance and excellent ultraviolet shielding effect. The object is to provide a fluorescent coloring synthetic resin molding.
Another object of the present invention is to provide a method for smoothly and easily producing the fluorescent color-forming synthetic resin molding described above.

  The inventors of the present invention have continually studied to achieve the above-described object. As a result, a polyvinyl alcohol resin is used as a synthetic resin, and a film, fiber, or other molded body is produced in advance from the polyvinyl alcohol resin, and the polyvinyl alcohol resin molded body is converted into a fluorescent metal compound. After immersing in a liquid containing metal ions to be formed, or after immersing in a liquid containing metal ions and activator ions, ions that react with the metal ions to form a metal compound that emits fluorescence under ultraviolet irradiation. It has been found that, when immersed in a liquid containing, phosphor fine particles made of a metal compound that emits fluorescence under irradiation of ultraviolet rays can be formed and dispersed in ultrafine particles having an average particle size of 50 nm or less in a polyvinyl alcohol-based resin molded body. .

And the said polyvinyl-alcohol-type resin molding in which the fluorescent substance fine particle with an average particle diameter of 50 nm or less was formed inside reacts with the said metal ion which forms the metal compound which emits fluorescence, and forms a metal compound which emits fluorescence Immersion treatment by immersion in a liquid containing the ions, or immersion in a liquid containing the ions and activator ions that react with the metal ions to form a metal compound that emits fluorescence and forms a metal compound that emits fluorescence When the aging treatment is performed, the crystallinity of the phosphor fine particles having an average particle diameter of 50 nm or less made of the metal compound is improved, and the concentration in the molded body is increased to increase the fluorescence emission intensity, thereby the fluorescence emitting strong fluorescence. It has been found that a chromogenic polyvinyl alcohol-based resin molding can be obtained.
Furthermore, when the above-described method is used, the present inventors have prepared a fluorescent coloring polyvinyl alcohol containing phosphor fine particles having an average particle size of 30 nm or less, further 20 nm or less dispersed in a synthetic resin molded body. It has been found that a resin-based molded product can be formed smoothly.

  In general, it is known that a polyvinyl alcohol-based polymer forms a complex with a transition metal ion via its hydroxyl group (see, for example, Non-Patent Document 1). The present inventors paid attention to this behavior unique to polyvinyl alcohol-based polymers, tried to finely disperse phosphor fine particles inside a molded body made of polyvinyl alcohol-based polymer, and had an average particle size of Thus, a fluorescent color-forming molded article containing phosphor fine particles of 50 nm or less in a finely dispersed state in the molded article could be obtained. That is, a molded body made of a polyvinyl alcohol-based polymer is first immersed in a liquid containing a metal ion that forms a fluorescent metal compound or a liquid containing the metal ion and an activator ion. A coordination bond block (complex block) consisting of a polyvinyl alcohol polymer molecular chain and a metal ion having a length of several angstroms is formed, or from a polyvinyl alcohol polymer molecular chain, a metal ion and an activator ion. By forming a coordination bond block (complex block), and then immersing it in a liquid containing ions (sulfur ions, sulfide ions, etc.) that react with the metal ions to form a fluorescent coloring metal compound, Ultrafine phosphor particles made of a fluorescent coloring metal compound in the coordination bond block portion of several angstrom size By forming, a molded article of polyvinyl alcohol polymer in which nano-sized fine phosphor particles having an average particle diameter of 50 nm or less are dispersed inside the molded article without causing aggregation between the particles can be obtained. did it. The molded body thus obtained is further aged by immersing it in a liquid containing the metal ions and ions that react with the metal ions to form a fluorescent color-forming metal compound, and optionally further containing activator ions. By doing so, it was found that the intensity of the fluorescence emitted by the phosphor fine particles is increased.

  In addition, the present inventors use a metal compound that emits fluorescence having one or more emission peaks in a wavelength range of 350 to 700 nm under ultraviolet irradiation as the metal compound that forms the phosphor fine particles. It is desirable from the point of emitting fluorescence that can be easily visually recognized only when irradiated with ultraviolet rays, and as the metal compound, a reaction between a group 12 metal ion of the periodic table and a group 16 element ion of the periodic table As a liquid for immersing the polyvinyl alcohol-based resin molded article, a liquid containing group 12 metal ions or a liquid containing group 12 metal ions and activator ions is preferable. And an average particle size in the polyvinyl alcohol-based resin molded body by successive immersion treatment using a liquid containing an ion containing a group 16 element. Phosphor fine particles having a thickness of 0 nm or less are formed, and then ripened with a solution containing a group 12 metal ion and an ion containing a group 16 element, or a group 12 metal ion, an activator ion, and a group 16 It has been found that it is preferable to perform aging treatment with a liquid containing ions containing these elements.

  Furthermore, the inventors of the present invention preferably perform the aging treatment at a temperature of 30 to 90 ° C. for 30 minutes or more in order to obtain a fluorescent coloring polyvinyl alcohol resin molded product that emits strong fluorescence, or the immersion treatment and The concentration of the metal ion generating compound in the liquid used for the aging treatment, the ion generating compound that reacts with the metal ion to form a metal compound that emits fluorescence under ultraviolet irradiation, and the concentration of the activator ion generating compound is within a predetermined range. Has been found to be preferable from the viewpoints of adjusting the particle diameter of the phosphor fine particles formed in the polyvinyl alcohol-based resin molded body and adjusting the concentration of the phosphor fine particles, and the present invention has been completed based on these findings.

That is, the present invention
(1) A polyvinyl alcohol resin in which a polyvinyl fine particle having a mean particle diameter of 50 nm or less that emits fluorescence in a wavelength range of 350 to 700 nm under irradiation of ultraviolet rays is formed in a polyvinyl alcohol resin molded body. It is a fluorescent color-forming polyvinyl alcohol-based resin molded article that is contained in a state of being dispersed in a proportion of 0.5% by mass or more based on the mass of the polymer.
further,
(2) The fluorescent color-forming polyvinyl alcohol-based resin molded article according to (1), wherein the average particle diameter of the phosphor fine particles is 30 nm or less;

(3) The phosphor fine particles are phosphor fine particles made of a metal compound (F) in which a group 16 element is bonded to a group 12 metal of the periodic table, which is doped or not doped with an activator (1) Or (2) a fluorescent color-forming polyvinyl alcohol resin molded article;
(4) The phosphor fine particles are phosphor fine particles made of a metal compound (F) in which a group 16 element is bonded to a group 12 metal of the periodic table doped with an activator, and the amount of the activator is In the fluorescent coloring polyvinyl alcohol-based resin molded article according to any one of (1) to (3), the amount is 0.001 mol or more with respect to 1 mol of the Group 12 metal element in the periodic table before doping the activator. Yes;
(5) At least one of phosphor fine particles mainly composed of zinc sulfide which is doped or not doped with an activator and phosphor fine particles mainly composed of cadmium sulfide which is not doped or doped with an activator. A fluorescent color-forming polyvinyl alcohol-based resin molded article according to any one of (1) to (4), which is a seed;
(6) The fluorescence developing polyvinyl alcohol-based resin molded body according to any one of (1) to (5), wherein the polyvinyl alcohol-based resin molded body is a film or a fiber;
(7) The fluorescent color-forming polyvinyl alcohol-based resin molded article according to any one of (1) to (6), wherein an average transmittance of visible light having a wavelength of 400 to 760 nm is 50% or more;
(8) The fluorescent color-forming polyvinyl alcohol-based resin molded product according to (7), wherein the film has a transmittance of ultraviolet rays having a wavelength of 300 nm of 10% or less.

And this invention,
(9) (i) A liquid (Ia) containing a metal ion (A) that forms a metal compound (F) that emits fluorescence in a wavelength range of 350 to 700 nm under irradiation of ultraviolet rays. Or a liquid (Ib) containing the metal ion (A) and the activator ion (C);
(Ii) It is immersed in a liquid (II) containing ions (B) that react with the metal ions (A) to form a metal compound (F) that emits fluorescence in the wavelength region of 350 to 700 nm under irradiation of ultraviolet rays. Phosphor particles having an average particle diameter of 50 nm or less made of a metal compound (F) that emits fluorescence in a wavelength range of 350 to 700 nm under irradiation of ultraviolet rays are formed in a molded body made of a polyvinyl alcohol-based polymer;
(Iii) Immerse the molded body made of the polyvinyl alcohol polymer containing the phosphor fine particles formed in the step (ii) in the molded body in the liquid (IIIa) containing the metal ions (A) and ions (B). Or dipping in the liquid (IIIb) containing the metal ions (A), ions (B) and activator ions (C);
Production of a fluorescent color-forming polyvinyl alcohol-based resin molded article containing phosphor fine particles with an average particle diameter of 50 nm or less that are doped or not doped with an activator, characterized in that Is the method.

Furthermore, the present invention provides
(10) Liquid (Ia), Liquid (Ib), Liquid (II), Liquid (IIIa), and Liquid (IIIb) are water, an organic solvent that swells a polyvinyl alcohol polymer, or water and a polyvinyl alcohol polymer The production method of the above (9), wherein the solvent is a mixed solvent of an organic solvent that swells
(11) The production method according to (9) or (10), wherein the aging treatment in the step (iii) is performed at a temperature of 30 to 90 ° C. for 30 minutes or more;
(12) The content of the metal ion (A) generating compound in the liquid (Ia) and the liquid (Ib) is 0.1 to 120 g / L, and the content of the activator ion (C) generating compound in the liquid (Ib) Is 0.1 to 120 g / L, and the content of the ion (B) -forming compound in the liquid (II) is 1 to 120 g / L (provided that the metal ions in the liquid (Ia) and the liquid (Ib) (A Any of the content of the product compound and the content of the ion (B) product compound in the liquid (II) is 5 g / L or more.) The metal ion (A) in the liquid (IIIa) and the liquid (IIIb) Content of product compound is 0.1-120 g / L and content of ion (B) product compound is 0.1-120 g / L, and content of activator ion (C) product compound in liquid (IIIb) Is 0.1 to 120 g / L The (9) in any one of - (11) located in the manufacturing method described;
(13) The production according to any one of (9) to (12), wherein the metal ion (A) is an ion of a group 12 metal of the periodic table and the ion (B) is an ion of an element of a group 16 of the periodic table Is a method;
(14) The metal ion (A) is zinc ion or cadmium ion, the ion (B) is sulfur ion, and the activator ion (C) is manganese ion, copper ion, silver ion, gold ion or rare earth element ion. It is a manufacturing method of any one of the above (9) to (13), which is at least one kind.

The fluorescent color-forming polyvinyl alcohol-based resin molded article of the present invention contains phosphor fine particles having an average particle size of 50 nm or less dispersed in the molded article without causing aggregation between the phosphor fine particles. For this reason, it is difficult to see under visible light, and emits fluorescence with high light intensity under ultraviolet irradiation.
Moreover, the fluorescent color-forming polyvinyl alcohol-based resin molded article of the present invention has a high visible light transmittance and excellent transparency, and has a low ultraviolet transmittance and excellent ultraviolet shielding properties.
Therefore, the fluorescent color-forming polyvinyl alcohol-based resin molded article of the present invention takes advantage of these characteristics, for example, anti-counterfeiting materials such as banknotes, securities paper, confidential documents, product tags, wallpaper, carpets, clothing, glass Extremely effective for various applications such as materials that combine UV shielding and decorative properties, such as interlayer films and films for glass application, and sensing materials that utilize the fact that fluorescence coloring changes due to surface adsorption of gases such as oxygen Can be used.

  By the production method of the present invention, a fluorescent color-forming polyvinyl alcohol-based resin molded article having the above-described excellent characteristics can be produced smoothly. Specifically, it is immersed in a solution containing a metal ion that forms a metal compound that emits fluorescence, or is immersed in a solution containing the metal ion and an activator ion, and then reacts with the metal ion to react with ultraviolet rays. A liquid containing the ions that form a metal compound that emits fluorescence by immersing in a liquid containing ions that form a metal compound that emits fluorescence under irradiation and then react with the metal ions that form a metal compound that emits fluorescence. Immersion treatment is performed by immersing in a solution containing the metal ions that form a fluorescent metal compound and a metal compound that reacts with the metal ions to form fluorescence and an activator ion. By adopting the process, a fluorescent material made of a metal compound that emits fluorescence under irradiation of ultraviolet rays is formed in the polyvinyl alcohol-based resin molded body. The body fine particles can be formed and dispersed in the form of fine particles having an average particle size of 50 nm or less, the crystallinity of the phosphor fine particles is improved, and the concentration of the phosphor fine particles is also increased. An alcohol-based resin molded body can be obtained.

It is the photograph which image | photographed the cut surface which cut | disconnected the PVA film which contains the fluorescent substance fine particle inside in Example 1 in the thickness direction with the transmission electron microscope (TEM). It is the photograph which image | photographed the cut surface of the surface vicinity which cut | disconnected the PVA film which contains the fluorescent substance fine particle inside in Example 1 in the thickness direction with the scanning electron microscope (SEM). The graph which shows the measurement result of the light transmittance in the wavelength range (ultraviolet ray-visible light region) of 200-800 nm of the PVA film which contains the fluorescent substance microparticles | fine-particles obtained by Example 1, the comparative example 1, and the comparative example 2 inside. It is. It is a graph which shows the fluorescence spectrum at the time of irradiating the excitation wavelength (ultraviolet ray) of 320 nm to the PVA film which contains the fluorescent substance microparticles | fine-particles obtained in Examples 1-3 and Comparative Example 2 inside. It is the photograph which image | photographed the cut surface which cut | disconnected the PVA film which contains the fluorescent substance fine particle inside in the thickness direction in the comparative example 1 with the transmission electron microscope (TEM).

The present invention is described in detail below.
The fluorescent coloring polyvinyl alcohol-based resin molded product of the present invention (hereinafter, polyvinyl alcohol is referred to as “PVA”) is contained in the molded product in a state where fluorescent fine particles that emit fluorescence under ultraviolet irradiation are dispersed. .
The degree of polymerization of the PVA polymer constituting the fluorescent color-forming PVA resin molded product of the present invention is not particularly limited, but considering the mechanical properties and dimensional stability of the fluorescent colorable PVA resin molded product, The porous PVA resin molded product is formed of a PVA polymer having an average degree of polymerization (viscosity average degree of polymerization determined according to JIS K6726 from the viscosity of an aqueous solution of a PVA polymer at 30 ° C.) of 1200 to 20000. preferable. The higher the polymer of the PVA polymer constituting the fluorescent coloring PVA resin molded body, the better because the strength and heat and humidity resistance of the molded body are better, but considering the production cost, molding cost, etc. of the PVA polymer Then, it is more preferable that the PVA-based resin molded body is formed from a PVA-based polymer having an average degree of polymerization of 1500 to 8000.

The saponification degree of the PVA polymer constituting the fluorescent color-forming PVA resin molded article of the present invention is not particularly limited, but the saponification degree is 88 mol% or more from the viewpoint of mechanical properties of the molded article. It is preferable that it is 90 mol% or more, and it is still more preferable that it is 96-99.9 mol%.
If the degree of saponification of the PVA polymer is low, it is not preferable from the viewpoints of process passability during molding, molding cost, mechanical properties of the fluorescent coloring PVA resin molding, and the like.

If the PVA polymer constituting the fluorescent color-forming PVA resin molding of the present invention is a PVA polymer mainly composed of vinyl alcohol units, a homopolymer of a vinyl ester of a carboxylic acid such as vinyl acetate is saponified. May be a PVA polymer consisting only of vinyl alcohol units or consisting only of vinyl alcohol units and a small amount of unsaponified carboxylic acid vinyl ester units, or as long as the effects of the present invention are not impaired. Further, it may be a vinyl alcohol copolymer having a small amount (usually at a ratio of 12 mol% or less) mainly composed of vinyl alcohol units and having other copolymer units as required. Other copolymer units in that case include, for example, olefins such as ethylene, propylene, and butylene, acrylic acid, acrylate, methyl acrylate and other acrylate esters, methacrylic acid, methacrylate, and methacrylic acid. (Meth) acrylamides such as methyl and other methacrylic esters, acrylamide, N-methylacrylamide, methacrylamide, N-methylolmethacrylamide, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, and other N- Vinyl amides, allyl ethers having polyalkylene oxide in the side chain, vinyl ethers such as methyl vinyl ether, nitriles such as acrylonitrile, vinyl halides such as vinyl chloride, maleic acid, maleate, maleic anhydride Phosphate, can be mentioned a copolymerization unit derived from such unsaturated carboxylic acid or its derivatives such as maleic acid esters. The PVA polymer constituting the fluorescent color-forming PVA resin molded product of the present invention can have one or more of the above copolymerized units. The above-mentioned copolymer unit may be introduced into the PVA polymer by copolymerization when producing the PVA polymer, or after the PVA polymer is produced, it is converted into the PVA polymer by a post reaction. It may be introduced.
However, the PVA polymer constituting the fluorescent color-forming PVA resin molded article of the present invention is a PVA polymer having a vinyl alcohol unit content of 88 mol% or more, particularly 90 mol% or more. This is preferable from the viewpoints of process passability during production of the body, molding cost, and mechanical properties of the molded body.

The phosphor fine particles contained in the fluorescent color-forming PVA resin molded body of the present invention are phosphor fine particles having an average particle diameter of 50 nm or less that emits fluorescence in a wavelength range of 350 to 700 nm under irradiation of ultraviolet rays. The fine particles are finely dispersed in the PVA resin molded body.
Here, in the present invention, the “ultraviolet rays” irradiated for generating fluorescence in the phosphor fine particles refers to light having a wavelength range of 1 to 390 nm, which is generally handled as ultraviolet rays.
The ultraviolet rays irradiated to the phosphor fine particles may be ultraviolet rays having a predetermined single wavelength within the ultraviolet wavelength range, or two or more ultraviolet rays having a predetermined single wavelength having different wavelengths within the ultraviolet wavelength range. May be combined, or may be ultraviolet light having an intensity distribution having one intensity peak or two or more intensity peaks in the ultraviolet wavelength range, or particularly an intensity peak. Any of the ultraviolet rays within the ultraviolet wavelength range may be used.

Further, the “fluorescent fine particles emitting fluorescence in the wavelength range of 350 to 700 nm under the irradiation of ultraviolet rays” contained in the fluorescent color-forming PVA resin molding of the present invention is 350 to 700 nm when irradiated with the ultraviolet rays. Any phosphor fine particles may be used as long as they emit fluorescence in the above wavelength range. The phosphor fine particles are different from each other in the wavelength range of 350 to 700 nm even when the phosphor fine particles emit fluorescence having a predetermined single wavelength in the wavelength range of 350 to 700 nm when irradiated with the ultraviolet rays, for example. Phosphor fine particles that emit fluorescence of two or more predetermined single wavelengths, or phosphors that emit fluorescence with intensity distribution having one or more intensity peaks in a wavelength range of 350 to 700 nm Fine particles may be used, or phosphor fine particles that emit fluorescence in a wavelength range of 350 to 700 nm with no particular intensity peak may be used.
Among them, the fluorescent color-forming PVA-based resin molded article of the present invention has one or more intensity peaks, particularly one intensity peak in the wavelength range of 400 to 650 nm under irradiation with ultraviolet rays having a wavelength of 200 to 390 nm. It is preferable from the viewpoint of the visibility of fluorescent color development that it contains one kind or two or more kinds of phosphor fine particles that emit fluorescence.

The fluorescent fine particles contained in the fluorescent color-forming PVA resin molded body of the present invention have an average particle size of 50 nm or less, preferably 30 nm or less, and more preferably 20 nm or less.
Here, the average particle diameter of the phosphor fine particles in this specification is based on a photograph obtained by photographing a fluorescent color-forming PVA-based resin molded article containing the phosphor fine particles with a transmission electron microscope (TEM). The average particle diameter of the phosphor fine particles calculated is a specific calculation method as described in the following examples.

The magnitude of light scattering by particles smaller than the wavelength of light is a function of the particle size, as represented by the Rayleigh scattering equation (see Non-Patent Document 2). The most important factor to make it smaller.
In the fluorescent color-forming PVA resin molded product of the present invention, the phosphor fine particles contained in the molded product are fine particles whose average particle size is an order of magnitude smaller than the wavelength of visible light (generally wavelength 380 to 780 nm) is 50 nm or less. When visible light is irradiated, the diffraction and scattering of the visible light are extremely reduced. As a result, the fluorescent color-forming PVA resin molded product of the present invention has a high visible light transmittance (transparency), and it is not visible under visible light that phosphor fine particles are contained, but under visible light. Low visibility of the phosphor fine particles is achieved.
On the other hand, a conventional molded article containing phosphor fine particles having an average particle size of 1 μm or more (1000 nm or more) is a phosphor fine particle having an average particle size one digit larger than the wavelength of visible light. Scattering and diffraction increase, and the presence of phosphor fine particles in the PVA-based resin molded body is easily visible under visible light, so that low visibility is not achieved, and the PVA-based resin molded body is visible. Light transmittance is low and transparency is poor.

Furthermore, in the fluorescent color-forming PVA resin molded product of the present invention, the average particle size of the phosphor fine particles contained in the molded product is 50 nm or less, which is combined with the achievement of low visibility under visible light. An increase in strength is achieved.
In general, it is known that when the semiconductor particle size is made nano-sized, the band gap increases, and the quantum mechanical behavior is different from that of a large particle of micron-sized or larger. This effect is called a quantum size effect. In particular, in the case of semiconductor fine particles that emit fluorescence, the fluorescence intensity increases as the quantum yield increases (for example, see Non-Patent Document 3).
In the present invention, the phosphor fine particles to be contained in the PVA-based resin molded body can be fluorescent color-forming semiconductor fine particles having an average particle size of 10 nm or less. In that case, a small amount of the phosphor fine particles are contained in the molded body. By containing, a molded body that emits strong fluorescence when irradiated with ultraviolet rays can be obtained.

The fluorescent color-forming PVA resin molded article of the present invention contains phosphor fine particles in a proportion of 0.5% by mass or more based on the mass of the PVA polymer constituting the molded article. It is preferable to contain in the ratio of 50 mass%, It is more preferable to contain in the ratio of 0.5-30 mass%, It is still more preferable to contain in the ratio of 1-10 mass%.
When the content of the phosphor fine particles in the PVA-based resin molded body is too small, the visibility under visible light can be lowered, but the fluorescence intensity is reduced when irradiated with ultraviolet rays, which is not preferable. On the other hand, when the content of the phosphor fine particles in the PVA-based resin molded body is too large, the visibility under visible light is increased, and the mechanical properties of the PVA-based resin molded body are easily deteriorated.

The phosphor fine particles contained in the fluorescent color-forming PVA-based resin molded body of the present invention are preferably phosphor fine particles based on semiconductor nanoparticles having an average particle size of 50 nm or less.
Phosphor fine particles based on semiconductor nanoparticles include metal compounds in which Group 16 elements are bonded to Group 12 metals in the periodic table (Group 12-16 compounds) [for example, zinc sulfide (ZnS), zinc oxide (ZnO). , Zinc selenide (ZnSe), zinc telluride (ZnTe), cadmium sulfide (CdS), cadmium selenium (CdSe), cadmium tellurium (CdTe), etc.], Group 14 element of periodic table (Si etc.) ) Phosphor fine particles, phosphor fine particles composed of a metal compound (group 13-15 compound) in which a group 15 element is bonded to a group 13 metal in the periodic table (indium phosphide (InP), gallium nitride (GaN), etc.) ] And so on.
Among these, phosphor fine particles composed of a metal compound (group 12-16 compound) in which a group 16 element is bonded to a group 12 metal of the periodic table, that is, zinc sulfide (ZnS) and zinc oxide (ZnO) described above. Zinc selenide (ZnSe), zinc telluride (ZnTe), cadmium sulfide (CdS), cadmium selenium (CdSe), cadmium tellurium (CdTe), etc. have high ionic crystallinity and optically direct transition. To preferred.
Among them, the phosphor fine particles are not doped or doped with an activator from the viewpoint of the fluorescence characteristics and the ease of production of the fluorescent color-forming PVA resin molded product of the present invention containing the phosphor fine particles. Phosphor fine particles composed of ZnS and CdS doped or not doped with an activator are more preferable, and phosphor fine particles composed of ZnS doped or not doped with an activator are more preferable in that they are colorless.

The phosphor fine particles contained in the fluorescent color-forming PVA resin molded body of the present invention are phosphor fine particles doped with an activator as described above, or phosphor fine particles not doped with an activator. However, phosphor fine particles made of a 12-16 group compound such as zinc sulfide (ZnS) can develop intrinsic fluorescence by being doped with an activator.
The activator can be used according to the required fluorescence wavelength (emission color). Examples of the activator include copper (Cu), manganese (Mn), silver (Ag), and gold (Au). Metal ions of rare earth elements including europium (Eu) and ytterbium (Yb), and the like, and these metal ions can be used alone or in combination of two or more as activators. .
If necessary, a coactivator such as chlorine (Cl), bromine (Br), iodine (I), or aluminum (Al) may be doped.
Then, by appropriately selecting the type of the activator that can provide these unique colors, a fluorescent color-forming PVA-based resin molded product that produces desired fluorescence can be obtained.
When the phosphor fine particles to be contained in the PVA-based resin molded body are phosphor fine particles doped with an activator, particularly phosphor fine particles composed of a 12-16 group compound doped with an activator, the amount of the activator is From the viewpoint of the activation effect and uniformity of the activator, it is preferably 0.001 mol or more, particularly 0.005 to 0.05 mol, relative to 1 mol of the metal compound before doping the activator.

The type, shape, and structure of the fluorescent color-forming PVA-based resin molded body of the present invention are not particularly limited and may be any molded body that can be manufactured using a PVA-based polymer. For example, a film, a sheet, a plate, a pipe , Tubes, rod-like bodies, granular bodies, various irregularly shaped bodies, fibers, woven fabrics, knitted fabrics, non-woven fabrics, papers and the like.
In the fluorescent color-forming PVA-based resin molded body of the present invention, it is desirable that the phosphor fine particles are contained in a substantially uniformly dispersed state in the molded body. It may be contained in a state where it is unevenly distributed in the place.
And it is disperse | distributing substantially uniformly, when the cut surface of a PVA-type resin molding is observed with a transmission electron gas microscope (TEM) or a scanning electron gas microscope (SEM), it is fluorescent microparticles | fine-particles. It is judged that the agglomerates and uneven distribution are not substantially observed.

The fluorescent color-forming PVA-based resin molded body of the present invention is prepared in advance from a PVA-based polymer, and the molded body is sequentially subjected to the immersion treatments of step (i) and step (ii), and then the step. Since it is smoothly manufactured by the manufacturing method of the present invention in which the aging treatment of (iii) is performed, when the thickness and size of the molded body are small, the phosphor fine particles are substantially uniform inside the PVA resin molded body. A PVA-based resin molded product dispersed in the resin can be obtained. On the other hand, when the molded body is thick, it is possible to obtain a PVA-based resin molded body in which many phosphor fine particles are dispersed in the molded body close to the surface of the PVA-based resin molded body.
Furthermore, the average visible light transmittance of the fluorescent color-forming PVA-based resin molded article of the present invention is preferably higher. Particularly, in the case of a film, the average visible light transmittance is 50% or more, preferably 60%. More preferably, it is 70% or more, and most preferably 80% or more.
The lower the transmittance of ultraviolet rays, the better from the viewpoint of the ultraviolet shielding function. Particularly, in the case of a film, the transmittance at a wavelength of 300 nm is 10% or less, preferably 1% or less, more preferably 0.5% or less. Most preferably, it is 0.1% or less.

  When the fluorescent color-forming PVA resin molded product of the present invention is a molded product such as a film, a sheet, or a plate, it is colorless and transparent under visible light, and the presence of fluorescent fine particles is not visually recognized. Since the fine particles emit fluorescence, the fluorescent coloring property can be imparted without impairing the visual information of the target object, for example, by attaching it to the target object as an anti-counterfeiting countermeasure material, a decoration material, a sensing material, or the like.

  When the fluorescent color-forming PVA resin molded product of the present invention is a fiber, the original color tone of the PVA fiber is visible as it is under visible light, and the fluorescent color-producing fiber emits fluorescence under ultraviolet irradiation. Therefore, as a material for preventing counterfeiting, a decoration material, a sensing material, and the like, for example, the fluorescent coloring PVA fiber is sewn into a cloth product, or a woven or knitted fabric using the fluorescent coloring PVA fiber. By manufacturing cloth, non-woven fabric, making paper by embedding the fluorescent coloring PVA fiber, and kneading the fluorescent coloring PVA fiber into a polymer, Fluorescence coloring property can be imparted without impairing the visual information of the object.

  The fluorescent color-forming PVA resin molded product of the present invention is within the range not impairing the effects of the present invention, together with phosphor fine particles, if necessary, an antioxidant, an antifreezing agent, a pH adjuster, a concealing agent, It may contain a coloring agent, an oil agent, a flame retardant, a special functional agent, and the like.

  The fluorescent color-forming PVA-based resin molded article of the present invention comprises: (i) a metal compound (F) that emits fluorescence in a wavelength range of 350 to 700 nm under irradiation of ultraviolet rays from a molded article prepared in advance using a PVA-based polymer. Soaked in the liquid (Ia) containing the metal ion (A) forming the metal or the liquid (Ib) containing the metal ion (A) and the activator ion (C), and then (ii) the metal ion It is immersed in a liquid (II) containing ions (B) that form a metal compound (F) that reacts with (A) and emits fluorescence in the wavelength range of 350 to 700 nm under irradiation of ultraviolet rays, and is made of a PVA polymer. In the molded body, fluorescent fine particles having an average particle diameter of 50 nm or less made of a metal compound (F) that emits fluorescence in a wavelength range of 350 to 700 nm under irradiation of ultraviolet rays are generated, and (iii) in the step (ii) Fluorescence formed A molded body made of a PVA polymer containing fine particles in the molded body is immersed in the liquid (IIIa) containing the metal ions (A) and ions (B), or the metal ions (A) and ions (B ) And activator ion (C) in the liquid (IIIb), and is smoothly produced by the production method of the present invention in which aging treatment is performed.

  Molded product made of PVA polymer before performing step (i) used in the production method of the present invention [hereinafter, molded product made of PVA polymer before the treatment of steps (i) to (iii). The production method of “sometimes simply referred to as“ PVA molded body ”] is not particularly limited, and may be produced by an appropriate method according to the type of PVA molded body or the type of PVA polymer forming the PVA molded body. For example, dry film formation, wet film formation, wet dry film formation, extrusion molding under blow, blow molding, inflation molding, coextrusion molding, injection molding, transfer molding, lamination molding, dry spinning, dry wet spinning, wet spinning It can be produced by melt spinning or the like.

  When the PVA molded body before the treatment of step (i) is a film, as a PVA film, a stock solution prepared by dissolving a PVA polymer in water, an organic solvent or a mixed solvent of water and an organic solvent is used as a metal roller or belt. PVA films obtained by casting and drying are preferably used. At that time, if a surfactant is added to the stock solution of the PVA polymer, the film-forming property is improved and the occurrence of thickness unevenness is suppressed, and from the metal roller or belt used for film formation. The film can be easily peeled off. The type of the surfactant is not particularly limited, but an anionic surfactant or a nonionic surfactant is preferably used, and a nonionic surfactant is more preferably used from the viewpoint of releasability such as a metal roller or a belt. In that case, as the anionic surfactant, for example, a carboxylic acid type such as potassium laurate, a sulfate type such as octyl sulfate, and a sulfonic acid type anionic surfactant such as dodecylbenzenesulfonate are suitable. Nonionic surfactants include, for example, alkyl ether types such as polyoxyethylene oleyl ether, alkylphenyl ether types such as polyoxyethylene octylphenyl ether, alkyl ester types such as polyoxyethylene laurate, polyoxyethylene, and the like. Alkylamine type such as laurylamino ether, alkylamide type such as polyoxyethylene lauric acid amide, polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether, alkanolamide type such as oleic acid diethanolamide, polyoxyalkylene allylphenyl An allyl phenyl ether type nonionic surfactant such as ether is preferred. These surfactants can be used alone or in combination of two or more.

When the PVA molded body before the treatment of the step (i) is a fiber, as a PVA fiber, a dry solution obtained by dissolving a PVA polymer in water, an organic solvent or a mixed solvent of water and an organic solvent, Fibers spun by dry and wet spinning, wet spinning, etc. are preferably used. Examples of the solvent used for preparing the stock solution include water, dimethyl sulfoxide (hereinafter abbreviated as “DMSO”), dimethylacetamide (hereinafter abbreviated as “DMAc”), dimethylformamide (hereinafter abbreviated as “DMF”), Examples thereof include polar solvents such as N-methylpyrrolidone (hereinafter abbreviated as “NMP”), polyhydric alcohols such as glycerin and ethylene glycol, and these solvents are used alone or in admixture of two or more. be able to. The stock solution may contain one or more swellable metal salts such as rhodan salts, lithium chloride, calcium chloride, and zinc chloride. Among them, suitable solvents for the preparation of the stock solution are water, DMSO, a mixed solvent of water and DMSO, a mixed solvent of water and glycerin, etc., and these solvents have a low environmental load and are easy to recover. .
A fiber made of a PVA polymer can be obtained by discharging a spinning stock solution in which PVA is dissolved from a spinning nozzle and then drying or passing it through a poor solvent.

  In the production method of the present invention, in the step (i), the PVA molded body produced in advance is converted into a metal compound that emits fluorescence in the wavelength range of 350 to 700 nm under ultraviolet irradiation (hereinafter simply referred to as “fluorescent coloring metal compound”). It may be immersed in a liquid (Ia) containing the metal ion (A) forming (F) or in a liquid (Ib) containing the metal ion (A) and the activator ion (C). .

  The liquid (Ia) and liquid (Ib) used in the step (i) are the metal ions (A) entering the PVA molded body or the metal ions (A) entering the PVA molded body during the immersion treatment in the step (i). It is good to prepare using the solvent which has the swelling effect | action of a PVA molded object so that permeation of an activator ion (C) may be performed smoothly. From this point, the liquid (Ia) and the liquid (Ib) are water alone, an organic solvent that swells the PVA polymer, a mixed solvent of water and an organic solvent that swells the PVA polymer, and a swelling accelerator such as salts. It is preferable to prepare using the added solvent. In this case, examples of the organic solvent that swells the PVA polymer include alcohols such as methanol and ethanol, DMSO, DMAc, DMF, and NMP.

The liquid (Ia) or liquid (Ib) used in the treatment of the step (i) preferably has a swelling ratio of 20 to 300% by mass with respect to the PVA polymer forming the PVA molded body, and is preferably 30 to 250%. More preferably, it is mass%. If the swelling rate is too low, the metal ions (A) or the metal ions (A) and the activator ions (C) are not smoothly infiltrated into the PVA molded body, and the fluorescent color developing property in the PVA resin molded body The phosphor fine particles made of the metal compound (F) are hardly formed. On the other hand, if the swelling rate is too high, the PVA molded product is dissolved in the liquid (Ia) or the liquid (Ib), resulting in poor process passability. In extreme cases, the PVA molded product is in the liquid (Ia) or liquid It completely dissolves in (Ib), and a fluorescent coloring PVA resin molded product cannot be obtained.
Here, liquid (solvent) [(Ia) or liquid (Ib) used in step (i), liquid (II), liquid (IIIa) or liquid (II) used in step (ii) and step (iii) described below The swelling ratio of the PVA polymer according to IIIb)] refers to the swelling ratio obtained by the following method.

[Swelling ratio of PVA polymer by liquid (solvent)]
A PVA polymer (powder having an average particle size of 0.5 mm) W ₁ (g) used for the production of a PVA molded body was placed in 100 g of a liquid (solvent) and allowed to stand at a temperature of 25 ° C. for 24 hours. Filter using the filter paper (for analysis), sandwich the PVA polymer powder obtained by filtration between the upper and lower tissue papers, and press lightly to remove the liquid adhering to the surface of the powder. After removing, the mass (W ₂ ) (g) is measured, and the swelling ratio of the PVA polymer by the liquid (solvent) is determined from the following formula.

Swelling ratio (% by mass) = {(W ₂ −W ₁ ) / W ₁ } × 100 (1)

Content of the metal ion (A) -forming compound in the liquid (Ia) and the liquid (Ib), that is, the amount of the compound added to the liquid to form the metal ion (A) in the liquid (Ia) and the liquid (Ib). The content is preferably 0.1 to 120 g, more preferably 1 to 100 g, with respect to 1 L of liquid (Ia) or liquid (Ib) (1 L of liquid after addition of the compound or the like). Preferably, it is 1-95g.
In terms of the content of the metal ion (A) itself, not the content of the metal ion (A) -forming compound, the metal ion (A) is reduced to 0. 1 L with respect to 1 L of the liquid (Ia) and the liquid (Ib). It is preferable to contain in the ratio of 05-50g, It is more preferable to contain in the ratio of 0.5-45g, It is still more preferable to contain in the ratio of 1-40g.
If the content of the metal ion (A) [metal ion (A) generating compound] in the liquid (Ia) and the liquid (Ib) is too small, it becomes difficult to obtain a PVA-based resin molded article having a desired fluorescence coloring intensity, On the other hand, if the content of the metal ion (A) [metal ion (A) generating compound] is too large, the PVA molded product is immersed in the liquid (Ia) or the liquid (Ib) during the immersion treatment in the step (i). The adhesion of the metal ion (A) -generating compound to the apparatus or the apparatus to be transferred while being immersed is likely to cause poor processability.

The metal ion (A) generating compound added and contained in the liquid (Ia) and the liquid (Ib) is a metal that reacts with the ion (B) in the next step (ii) and emits fluorescence in the wavelength range of 350 to 700 nm. Any compound containing a metal ion (A) moiety that forms the compound (F) may be used, in particular, a salt of a group 12 metal in the periodic table, particularly an organic acid salt of zinc, an inorganic acid salt of zinc, an organic acid of cadmium. Acid salts and inorganic acid salts of cadmium are preferably used. More specifically, zinc acetate, zinc formate, zinc citrate, zinc benzoate, zinc sulfate, zinc nitrate, zinc chloride, zinc bromide and other zinc salts, cadmium acetate, cadmium formate, cadmium citrate, cadmium benzoate And cadmium salts such as cadmium sulfate, cadmium nitrate, cadmium chloride, and cadmium bromide.
In the liquid (Ia) and the liquid (Ib), only one kind of the above-described metal ion (A) generating compound may be added, or two or more kinds may be added.
Among these, zinc or cadmium acetate, nitrate, sulfate, and chloride are preferably used because of their high solubility in the liquid (Ia) and liquid (Ib), and zinc acetate, zinc nitrate, zinc sulfate, and / or Alternatively, zinc chloride is more preferably used.

Further, the content of the activator ion (C) -producing compound in the liquid (Ib), that is, the content of the compound used to form the activator ion (C) in the liquid by adding to the liquid (Ib) is: It is preferably 0.1 to 120 g, more preferably 1 to 100 g, and more preferably 1 to 95 g based on 1 L of liquid (Ib) (1 L of liquid after addition of the compound or the like). Further preferred.
In terms of the content of the activator ion (C) itself, not the content of the activator ion (C) generating compound, the activator ion (C) is 0.05 to 1 L per 1 L of the liquid (Ib). It is preferable to contain in the ratio of 50g, It is more preferable to contain in the ratio of 0.5-45g, It is still more preferable to contain in the ratio of 1-40g.
If the content of the activator ion (C) [activator ion (C) generating compound] in the liquid (Ib) is too small, the activator ion (C) is less likely to provide an activator, while the activator ion (C ) When the content of the [activator ion (C) generating compound] is too large, a device for immersing the PVA molded body in the liquid (Ib) during the immersion treatment in the step (i), or a device for transferring while immersed. The activator ion (C) -generating compound adheres to the surface of the substrate and the like, and poor processability is likely to occur.

As an activator ion (C) generating compound to be added and contained in the liquid (Ib), an ion having an activating effect on the metal compound (F) emitting fluorescence in the wavelength range of 350 to 700 nm is generated in the liquid (Ib). Any compound may be used, for example, organic acid salts and inorganic acid salts of metals such as copper (Cu), manganese (Mn), silver (Ag), and gold (Au), europium (Eu), ytterbium (Yb ) And other organic acid salts, inorganic acid salts and oxides of rare earth elements (metals). More specifically, for example, copper organic acid salt or inorganic acid salt such as copper acetate, copper formate, cuprous chloride, cupric chloride, copper nitrate, copper sulfate, manganese acetate, manganese chloride, manganese nitrate, Manganese compounds such as manganese sulfate and manganese peroxide, silver compounds such as silver chloride, silver chloride, silver nitrate and silver sulfate (silver salts), gold compounds such as gold chloride and chloroauric acid, europium compounds and ytterbium compounds And so on.
In liquid (Ib), only 1 type of an activator ion (C) production | generation compound mentioned above may be added, or 2 or more types may be added.

The treatment of the step (i) in which the PVA molded body is immersed in the liquid (Ia) or the liquid (Ib) may be performed in a batch manner, or the PVA molded body is immersed in the liquid (Ia) and the liquid (Ib). However, you may carry out by the continuous type which lets it pass continuously.
Further, the entire PVA molded body is completely immersed in the liquid (Ia) or liquid (Ib), and activated with metal ions (A) or metal ions (A) from the entire periphery of the PVA molded body into the PVA molded body. The method of infiltrating the agent ion (C) is preferably employed, but in some cases, only a part of the PVA molded body is immersed in the liquid (Ia) or the liquid (Ib), and the inside of the immersed PVA molded body part Only the metal ion (A) or the metal ion (A) and the activator ion (C) may be allowed to enter. When the latter method is employed, a fluorescent color-forming PVA-based resin molded body in which phosphor fine particles are present only in a part of the PVA molded body is formed.

The temperature of the liquid (Ia) and the liquid (Ib) at the time of the immersion treatment in the step (i) is generally 10 to 70 ° C., particularly 20 to 50 ° C. It is preferable from the viewpoints of the penetration efficiency of A), the penetration efficiency of metal ions (A) and activator ions (C), the process passability of the PVA molded article, and the like.
If the immersion temperature is too low, the immersion of the metal ions (A) in the PVA molded body, or the immersion of the metal ions (A) and the activator ions (C) is reduced, or the immersion takes time. Salt tends to precipitate. On the other hand, when the immersion temperature is too high, the PVA molded body may be partially dissolved.
Further, the immersion time of the PVA molded body in the liquid (Ia) or liquid (Ib) can be adjusted according to the type, size, thickness, shape, temperature of the liquid, etc. of the PVA molded body, Generally, it is preferably 10 seconds or longer, more preferably 60 seconds or longer, and particularly preferably 300 to 900 seconds.

Next, the PVA molded body subjected to the immersion treatment in the step (i) is reacted with the metal ion (A) in the step (ii) and emits fluorescence in a wavelength range of 350 to 700 nm under irradiation of ultraviolet rays ( The average particle size of the metal compound (F) that immerses in the liquid (II) containing the ions (B) forming F) and emits fluorescence in the wavelength region of 350 to 700 nm under irradiation of ultraviolet rays in the PVA molded body. Phosphor fine particles having a size of 50 nm or less are generated.
The immersion treatment in the step (ii) may be performed after the PVA molded body subjected to the immersion treatment in the step (i) is washed with water, alcohol or the like, or directly during the washing without washing. Of these, it is preferable to perform directly without washing, since phosphor fine particles can be smoothly formed in the PVA molded body.

The liquid (II) used in the step (ii) is a solvent having a swelling action of the PVA molded body so that the ions (B) are smoothly infiltrated into the PVA molded body during the immersion treatment in the step (ii). It is good to prepare using. From this point, the liquid (II) swells water alone, an organic solvent that swells the PVA polymer, water and the PVA polymer, like the liquid (Ia) or liquid (Ib) used in the step (i). It is preferable to prepare a mixed solvent of organic solvents to be used and the above-mentioned solvent to which a swelling accelerator such as salts is added. Examples of the organic solvent to swell the PVA polymer include alcohols such as methanol and ethanol, DMSO, and DMAc. , DMF, NMP and the like.
Like the liquid (Ia) or (Ib) used in the step (i), the liquid (II) used in the step (ii) has a swelling ratio of 20 to 300% by mass with respect to the PVA polymer forming the PVA molded body. It is preferable that it is 30 to 250% by mass. If the swelling rate is too low, the infiltration of ions (B) into the PVA molded article will not be carried out smoothly, and it will be difficult to form phosphor fine particles composed of the fluorescent coloring metal compound (F) in the PVA resin molded article. . On the other hand, if the swelling rate is too high, the PVA molded product will be dissolved in the liquid (II) and the process passability will be poor, and in extreme cases, the PVA molded product will be completely dissolved in the liquid (II). As a result, a fluorescent coloring PVA resin molded article cannot be obtained.

The content of the ion (B) -forming compound in the liquid (II), that is, the content of the compound added to the liquid to form the ion (B) in the liquid (II) is 1 L of the liquid (II) The amount is preferably 1 to 120 g, more preferably 1 to 100 g, and still more preferably 1 to 95 g based on 1 L of the liquid after the addition of the compound.
In terms of the content of the ion (B) rather than the content of the ion (B) -forming compound, the ion (B) is contained at a ratio of 0.5 to 50 g with respect to 1 L of the liquid (II). Preferably, it is contained in a proportion of 1 to 45 g, more preferably 2 to 40 g.
If the content of the ion (B) [ion (B) generating compound] in the liquid (II) is too small, it becomes difficult to obtain a PVA-based resin molded product having the desired fluorescence intensity, while the ion (B) [ion If the content of (B) product compound] is too high, ions (such as a device for immersing the PVA molded body in the liquid (II) during the immersion treatment in step (ii) or a device for transferring while immersed ( B) The product compound is likely to adhere, resulting in poor processability. Further, the burden on the recovery system is increased, and the generation of odor is likely to increase.

  Further, when both the content of the metal ion (A) generating compound in the liquid (Ia) and the liquid (Ib) and the content of the ion (B) generating compound in the liquid (II) are small, PVA having a desired fluorescence coloring intensity Since it is difficult to obtain a resin-based resin molded body, either the content of the metal ion (A) generating compound in the liquid (Ia) and the liquid (Ib) or the content of the ion (B) generating compound in the liquid (II) It is preferably 5 g / L or more, more preferably 7 g / L or more, and still more preferably 10 g / L or more.

  As an ion (B) generating compound to be added / contained in the liquid (II), it reacts with the metal ion (A) already infiltrated (impregnated) into the PVA molded body by the immersion treatment in the step (i), and 350 Any compound may be used as long as it is a compound containing an ion (B) portion that forms phosphor fine particles made of a metal compound (F) that emits fluorescence in a wavelength range of ˜700 nm in a PVA molded body, and particularly, a group 16 element in the periodic table is selected. A compound containing sulfur is preferably used, and in particular, a compound containing sulfur, that is, a sulfur-containing compound that generates sulfur ions or sulfide ions in the liquid (II) is preferably used. Specific examples of the sulfur-containing compound preferably used as the ion (B) -generating compound include sodium sulfide, sodium dithionate, sodium thiosulfate, sodium hydrogen sulfite, sodium pyrosulfate, hydrogen sulfide, thiourea, thioacetamide, and the like. These compounds may be used alone or in combination of two or more. Among these, sodium sulfide is more preferably used from the viewpoints of cost, availability, and low corrosivity.

The treatment in the step (ii) of immersing the PVA molded body in the liquid (II) may be performed in a batch manner, or the PVA molded body that has been processed in the step (i) is immersed in the liquid (II). You may carry out by the continuous type which passes continuously in the state.
In addition, it is desirable to completely immerse the entire PVA molded body in the liquid (II) and allow the ions (B) to enter the PVA molded body from the entire periphery of the PVA molded body. When i) is processed by immersing only a part of the PVA molded body in the liquid (Ia) or liquid (Ib), only the part immersed in the step (i) is immersed in the liquid (II) The phosphor fine particles made of the fluorescent coloring metal compound (F) may be formed only inside the PVA molded body portion.

Since the reaction between the metal ions (A) impregnated in the PVA molded body in step (i) and the ions (B) (especially sulfur ions) is generally performed very quickly, the immersion in step (ii) Although there is no particular limitation on the time, in order to sufficiently infiltrate the ions (B) into the PVA molded body, the immersion time in the liquid (II) in the step (ii) is preferably 5 seconds or more. , More preferably 30 seconds or more, and still more preferably 150 to 600 seconds.
Further, the temperature of the liquid (II) at the time of the immersion treatment in the step (ii) is generally 10 to 70 ° C., particularly 20 to 50 ° C., so that the ions (B) enter the PVA molded body. It is preferable from the viewpoints of efficiency and process passability of the PVA compact.

In the present invention, after the immersion treatment in step (i) is performed only once, the immersion treatment in step (ii) may be performed only once to perform the next step (iii) (aging treatment), or After the immersion treatment in step (i) and the immersion treatment in step (ii) are alternately repeated a plurality of times (for example, 2, 3, 4, 5 or more times), the next step (iii) ( Aging treatment) may be performed.
By repeating step (i) and step (ii) alternately a plurality of times, the content of the phosphor fine particles in the PVA molded body can be increased.
In the present invention, either or both of the immersion treatment in step (i) and the immersion treatment in step (ii) may be performed without applying ultrasonic waves, or may be performed while applying ultrasonic waves. When it is carried out while applying ultrasonic waves, the adhesion of phosphor fine particles to the surface of the PVA molded body is reduced, and a fluorescent color-forming PVA resin molded body having a good appearance can be obtained.

Fluorescent coloring PVA containing phosphor fine particles having an average particle size of 50 nm or less dispersed in the PVA molded body by performing the immersion treatment in the above-described steps (i) and (ii) A molded body is formed.
Furthermore, in the present invention, in the next step (iii), the PVA molded body containing the phosphor fine particles obtained in the step (ii) in the molded body contains the metal ions (A) and ions (B). It is immersed in liquid (IIIa) and aged, or is immersed in liquid (IIIb) containing metal ions (A), ions (B) and activator ions (C).
The aging treatment in the step (iii) may be performed after washing the PVA molded body obtained in the step (ii) to remove the phosphor fine particles adhering to the surface of the PVA molded body, or the process The aging treatment in step (iii) may be performed as it is without washing the PVA molded body obtained in (ii). Among them, it is preferable from the viewpoint of production cost to perform the aging treatment without washing.

  The liquid (IIIa) or liquid (IIIb) used in the step (iii) is the same metal ion (A) contained in the liquid (Ia) or liquid (Ib) used in the step (i) as the metal ion (A). It is desirable that the same ion (B) as that contained in the liquid (II) used in the step (ii) is contained as the ion (B). Further, the liquid (IIIb) used in the step (iii) contains the same activator ion (C) as that contained in the liquid (Ib) used in the step (i) as the activator ion (C). It is desirable. By doing so, the phosphor fine particles contained in the PVA molded body are aged, thereby improving the crystallinity of the phosphor fine particles, and the phosphor fine particles emit stronger fluorescence.

  The liquid (IIIa) and liquid (IIIb) used in the step (iii) are the ingress of metal ions (A), ions (B), and activator ions (C) into the PVA molded body in the aging treatment of the step (iii). Therefore, it is preferable to prepare a PVA molded body using a solvent having a swelling action so that the liquid (IIIa) and the liquid (IIIb) swell the water alone and the PVA polymer. It is preferable to prepare an organic solvent, a mixed solvent of water and an organic solvent that swells the PVA polymer, the above-described solvent to which a swelling accelerator such as salts is added, and an organic solvent that swells the PVA polymer. Can include alcohols such as methanol and ethanol, DMSO, DMAc, DMF, NMP and the like.

  The liquid (IIIa) or the liquid (IIIb) at the time of performing the treatment of the step (iii) has a swelling ratio of 20 with respect to the PVA polymer forming the PVA molded body, as in the steps (i) and (ii). It is preferable that it is -300 mass%, and it is more preferable that it is 30-250 mass%. If the swelling rate is too low, the metal ions (A), ions (B), and activator ions (C) are not smoothly infiltrated into the PVA molded body, and the fluorescence coloring property contained in the PVA resin molded body The aging treatment of the phosphor fine particles made of the metal compound (F) and the accompanying improvement in crystallinity are insufficient, and the fluorescent emission intensity of the phosphor fine particles is difficult to increase. On the other hand, if the swelling rate is too high, the PVA molded product will be dissolved in the liquid (IIIa) or the liquid (IIIb), resulting in poor process passability. It dissolves in (IIIb), and a fluorescent coloring PVA resin molded article cannot be obtained.

The content of the metal ion (A) -forming compound in the liquid (IIIa) and the liquid (IIIb) is 0 with respect to 1 L of the liquid (IIIa) or the liquid (IIIb) (1 L of the liquid after the compound or the like is added). 0.1 to 120 g is preferable, 1 to 100 g is more preferable, and 1 to 95 g is still more preferable.
In terms of the content of the metal ion (A) itself, not the content of the metal ion (A) -forming compound, the metal ion (A) is reduced to 0.1% with respect to 1 L of the liquid (IIIa) and the liquid (IIIb). It is preferable to contain in the ratio of 05-50g, It is more preferable to contain in the ratio of 0.5-45g, It is still more preferable to contain in the ratio of 1-40g.
If the content of the metal ion (A) [metal ion (A) forming compound] in the liquid (IIIa) and the liquid (IIIb) is too small, the phosphor fine particles contained in the PVA molded body are not sufficiently aged, and the phosphor If the intensity of the fluorescence emitted by the fine particles is not sufficiently high while the content of the metal ion (A) [metal ion (A) -forming compound] is too large, the PVA molded body is removed during the aging treatment in step (iii) ( Adhesion of the metal ion (A) generating compound to an apparatus for immersing in IIIa) and liquid (IIIb), an apparatus for transferring while immersing, and the like are likely to cause poor processability.

As the metal ion (A) -forming compound to be added and contained in the liquid (IIIa) and the liquid (IIIb), the group 12 metal salts in the periodic table are used in the same manner as described in the explanation of the step (i). Among them, in particular, an organic acid salt of zinc, an inorganic acid salt of zinc, an organic acid salt of cadmium, and an inorganic acid salt of cadmium are preferably used. The kind of the specific compound corresponding to it is the same as the various zinc salts and cadmium salts given as specific examples in the explanation of step (i).
Among these, zinc or cadmium acetate, nitrate, sulfate, and chloride are preferably used because of their high solubility in the liquid (IIIa) and liquid (IIIb), and zinc acetate, zinc nitrate, zinc sulfate and / or Alternatively, zinc chloride is more preferably used.

The content of the ion (B) -forming compound in the liquid (IIIa) and the liquid (IIIb) is 0. 1 L with respect to 1 L of the liquid (IIIa) or the liquid (IIIb) (1 L of the liquid after the addition of the compound or the like). It is preferably 1 to 120 g, more preferably 1 to 100 g, and still more preferably 1 to 95 g.
In terms of the content of the ion (B) rather than the content of the ion (B) -forming compound, 0.05 to 50 g of the ion (B) with respect to 1 L of the liquid (IIIa) and the liquid (IIIb). It is preferable to contain in the ratio of 0.5-45g, It is more preferable to contain in the ratio of 0.5-45g, It is still more preferable to contain in the ratio of 1-40g.
If the content of the ions (B) [ion (B) generating compound] in the liquid (IIIa) and the liquid (IIIb) is too small, the phosphor fine particles contained in the PVA molded body are insufficiently matured, If the intensity of the emitted fluorescence is not sufficiently high while the content of the ions (B) [ion (B) generating compound] is too large, the PVA molded product is removed from the liquid (IIIa) and the liquid during the aging treatment in step (iii). Adhesion of the ion (B) -generating compound to an apparatus for immersing in (IIIb) or an apparatus for transferring while immersing is likely to cause poor processability.

  The ion (B) generating compound to be added / contained in the liquid (IIIa) and liquid (IIIb) is a compound containing the same ion (B) part as that contained in the liquid (II) used in the step (ii). Preferably, a compound containing a group 16 element of the periodic table, particularly the same sulfur-containing compound as described in the above-mentioned explanation relating to step (ii) is used, and a specific example thereof is used in step (ii). This is as described in the explanation section.

Further, the content of the activator ion (C) -generating compound in the liquid (IIIb) is 0.1 to 120 g with respect to 1 L of the liquid (IIIb) (1 L of the liquid after adding the compound). Is more preferable, 1 to 100 g is more preferable, and 1 to 95 g is still more preferable.
In terms of the content of the activator ion (C) itself, not the content of the activator ion (C) generating compound, the activator ion (C) is 0.05 to 1 L per 1 L of the liquid (IIIb). It is preferable to contain in the ratio of 50g, It is more preferable to contain in the ratio of 0.5-45g, It is still more preferable to contain in the ratio of 1-40g.
If the content of the activator ion (C) [activator ion (C) generating compound] in the liquid (IIIb) is too small, the activator ion (C) is less likely to provide an activator, while the activator ion (C ) When the content of [activator ion (C) generating compound] is too large, an apparatus for immersing the PVA molded article in the liquid (IIIb) during the immersion treatment in the step (iii), or an apparatus for transferring while immersed. The activator ion (C) -generating compound adheres to the surface of the substrate and the like, and poor processability is likely to occur.

  The activator ion (C) generating compound to be added and contained in the liquid (IIIb) is the same compound as described above in the explanation of the liquid (Ib) used in the step (i), for example, copper (Cu), manganese Organic salts and inorganic acid salts of metals such as (Mn), silver (Ag) and gold (Au), organic acid salts and inorganic acids of rare earth elements (metals) including europium (Eu) and ytterbium (Yb) A salt, an oxide, or the like can be used, and specific examples are as described in the description of the liquid (Ib) used in the step (i).

The aging treatment of the step (iii) comprising immersing the PVA molded body in the liquid (IIIa) or the liquid (IIIb) may be performed in a batch manner, or the PVA molded body that has been subjected to the process of the step (ii). You may carry out by the continuous type which passes continuously, making it immerse in liquid (IIIa) and liquid (IIIb).
The aging treatment in the step (iii) is preferably performed by immersing the entire PVA molded body in the liquid (IIIa) or the liquid (IIIb). However, in some cases, the step (i) and the step (ii) are performed in the PVA. When only a part of the molded body is immersed in the liquid (Ia) or liquid (Ib) and further immersed in the liquid (II), only the part immersed in the step (i) and the step (ii) An aging treatment may be performed by dipping in the liquid (IIIa) or the liquid (IIIb).

As the temperature of the liquid (IIIa) and the liquid (IIIb) during the aging treatment in the step (iii) is higher, the dissolution and precipitation reaction rate of the phosphor fine particles contained in the PVA molded body is increased. Although it is preferable because the anisotropic growth rate of the primary particles of the fine particles is increased and the crystallinity is increased, if the liquid temperature is too high, there arises a problem that the PVA molded product is dissolved in the liquid (IIIa) and the liquid (IIIb). Therefore, generally 30-90 degreeC is preferable and 40-80 degreeC is more preferable.
In particular, when the liquid (IIIa) and the liquid (IIIb) are aqueous solutions, it is preferable to employ the above temperature.
The immersion time of the PVA molded body in the liquid (IIIa) or liquid (IIIb) during the aging treatment is preferably longer, but is generally preferably 30 minutes to 20 hours, and more preferably 1 to 5 hours. Increasing the aging time promotes anisotropic growth of the primary particles accompanying the dissolution and precipitation reaction of the phosphor fine particles, improving the crystallinity of the particles and improving the fluorescence emission intensity.

  The fluorescent color-forming PVA-based resin molded body having the phosphor fine particles that have undergone the aging treatment in the step (iii) inside can be improved in mechanical properties by drying or heat treatment. In general, the drying treatment or heat treatment of the fluorescent color-forming PVA-based resin molded body is preferably performed at a temperature of 70 to 250 ° C, more preferably at a temperature of 100 to 200 ° C. When the temperature is lower than the above range, drying becomes insufficient, and it is difficult to obtain the effect of improving the physical properties of the PVA resin molded product. On the other hand, when the temperature is higher than the above range, the fluorescent coloring PVA resin molded product is not obtained. The surface is partially melted and thermally decomposed, and the physical properties are likely to be lowered.

As described above, the fluorescent color-forming PVA resin of the present invention containing phosphor fine particles having an average particle diameter of 50 nm or less that emits fluorescence in a wavelength range of 350 to 700 nm under ultraviolet irradiation. A molded body is obtained.
The fluorescent color-forming PVA-based resin molded product of the present invention has an average particle size of phosphor fine particles contained in the molded product of 50 nm or less and is extremely fine and dispersed, so that it is difficult to visually recognize under visible light, On the other hand, it emits fluorescent light with high light intensity under ultraviolet irradiation, and also has high transmittance of visible light and excellent transparency. Taking advantage of these properties, for example, banknotes, securities paper, confidential documents, merchandise Anti-counterfeiting materials such as tags, wallpaper, carpets, clothing, glass interlayers, materials that combine UV shielding and decorative properties, such as film for glass application, and fluorescence coloring changes due to surface adsorption of gases such as oxygen It can be used extremely effectively for various applications such as sensing materials.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
In the following examples and the like, the content of phosphor fine particles in the PVA resin molded product, the amount of activator introduced, the average particle size of the phosphor fine particles, the visible light transmittance of the film, and the PVA resin molded product The fluorescence emission wavelength was determined as follows.

(1) Content of phosphor fine particles in the PVA-based resin molded body:
The content of phosphor fine particles (zinc sulfide particles doped with or without an activator) contained in the PVA-based resin molded body was measured using an ICP emission analyzer “IRIS-AP” manufactured by Jarrel Ash. It was measured. When the zinc sulfide particles (phosphor fine particles) are doped with an activator, the content of the phosphor fine particles is defined as the content of the entire zinc sulfide particles including the activator.

(2) Content of activator in phosphor fine particles contained in PVA resin molded body:
Based on the result of the ICP emission analysis of (1) above, the mol% of the activator element with respect to the zinc element of the phosphor fine particles (zinc sulfide) was determined and used as the activator content.

(3) Average particle diameter of phosphor fine particles contained in the PVA-based resin molded body:
A cross section of a PVA-based resin molded body (a cut surface obtained by cutting the film in the thickness direction when the molded body is a film, and a cut surface obtained by cutting the film perpendicularly to the length direction when the molded body is a fiber) Photographed using an electron microscope (TEM) (“H-800NA” manufactured by Hitachi, Ltd.) (magnification = 100,000 times), and all particles contained in a predetermined square portion centered on the intersection of diagonal lines of the photograph The maximum diameter of each was measured, and the average value was taken as the average particle diameter of the phosphor fine particles. At that time, the area of the “predetermined square portion” was an area in which almost 100 particles were included in the square portion.

(4) Visible light transmittance and ultraviolet light transmittance of the PVA-based resin molded body (film):
About PVA-type resin molding (film), using a self-spectrophotometer ("UV-2500PC" manufactured by Shimadzu Corporation), the PVA-based resin molding (film) has a wavelength range of 200 to 800 nm (ultraviolet to visible light). Area) was measured for light transmittance every 1.0 nm, and the average transmittance in the wavelength region (visible light region) of 400 to 760 nm was determined. Here, the average transmittance was obtained by dividing the sum of the light transmittances every 1 nm by the number of light transmittances measured.
Moreover, the transmittance | permeability of the ultraviolet-ray with a wavelength of 300 nm was calculated | required, and it was set as the parameter | index of an ultraviolet-ray shielding factor.

(5) Fluorescence emission wavelength of PVA resin molded product:
Using a fluorescence spectrophotometer (“RF-5300PC” manufactured by Shimadzu Corporation), the maximum absorption wavelength (peak wavelength) of the fluorescence emitted when the PVA resin molded product was irradiated with an excitation wavelength (ultraviolet light) of 320 nm. The fluorescence emission wavelength was used.

  Note that zinc acetate, cadmium acetate, manganese acetate, copper acetate and sodium sulfide used in the following Examples and Comparative Examples are all manufactured by Wako Pure Chemical Industries, Ltd.

Example 1
(1) PVA (viscosity average polymerization degree = 1700, saponification degree = 99.9 mol%) was dissolved in water to form an aqueous solution having a PVA concentration of 13% by mass, and this PVA aqueous solution was cast on a metal at 60 ° C. And dried at 50 ° C. for 3 hours to produce a PVA film having a thickness of 75 μm.
(2) The residence time of the PVA film obtained in the above (1) is 600 seconds in a water bath at a temperature of 25 ° C. composed of a zinc acetate aqueous solution with a zinc acetate concentration of 500 mM (91.8 g / L). After the immersion, the substrate was immersed in a water bath composed of a sodium sulfide aqueous solution having a sodium sulfide concentration of 250 mM (19.5 g / L) at a temperature of 25 ° C. under ultrasonic irradiation so that the residence time was 300 seconds.
(3) Next, the PVA film was taken out from a water bath made of an aqueous sodium sulfide solution, and the taken out PVA film was dissolved in a zinc acetate aqueous solution having a zinc acetate concentration of 500 mM (91.8 g / L) and a sodium sulfide concentration of 250 mM (19 (5 g / L) sodium sulfide aqueous solution mixed at a volume ratio of 1: 1 (zinc acetate concentration is 45.9 g / L, sodium sulfide concentration is 9.75 g / L) (aging solution) It was immersed in (temperature 70 ° C.) and held at 70 ° C. for 1 hour. Thereafter, the PVA film was taken out of the mixed solution, washed with water and methanol in this order, and dried with hot air at 50 ° C. to produce a PVA film containing zinc sulfide fine particles.

(4) The appearance of the PVA film obtained in the above (3) was smooth and good.
When the PVA film obtained in the above (3) was cut in the thickness direction and the cut surface was photographed with a transmission electron microscope (TEM), as shown in FIG. The body fine particles (zinc sulfide fine particles) were substantially uniformly dispersed inside the film without agglomeration.
Further, when the PVA film was cut in the thickness direction and the cut surface was photographed with a scanning electron microscope (SEM), as shown in FIG. 2, near the surface of the PVA film (a depth of about 150 nm from the surface). ), There were more phosphor particles than inside, but no aggregation of the phosphor particles was observed, and there was almost no adhesion to the surface of the film.
And based on the TEM photograph of FIG. 1, when the average particle diameter of the phosphor fine particles (zinc sulfide fine particles) contained in the PVA film was determined by the method described above, it was 8 nm.
(5) Further, the content of the phosphor fine particles contained in the PVA film obtained in the above (3) was determined by the above-described method and found to be 3.49% by mass.

(6) Furthermore, when the light transmittance in the wavelength range of 200 to 800 nm (ultraviolet ray to visible light region) was measured for the PVA film obtained in (3) above, it was as shown in FIG. It was. From FIG. 3, when the average transmittance in the wavelength range of 400 to 760 nm (visible light range) and the transmittance of ultraviolet light having a wavelength of 300 nm were determined by the above-described method, the average transmittance of visible light was 95%, The transmittance of visible light was high and the transparency was excellent. On the other hand, the transmittance of ultraviolet rays having a wavelength of 300 nm was as low as 0.1%, and the ultraviolet shielding properties were excellent.
(7) Further, when the PVA film obtained in (3) above was irradiated with an excitation wavelength (ultraviolet light) of 320 nm and measured for its fluorescence spectrum, it was as shown in FIG. The assigned maximum absorption was observed.

Example 2
(1) PVA (viscosity average polymerization degree = 1700, saponification degree = 99.9 mol%) was dissolved in water to form an aqueous solution having a PVA concentration of 13% by mass, and this PVA aqueous solution was cast on a metal at 60 ° C. The PVA film having a thickness of 75 μm was dried.
(2) The PVA film obtained in (1) above has a zinc acetate concentration of 133 mL (24.4 g / L) and a zinc acetate aqueous solution of 150 mL and a manganese acetate (activator) concentration of 8 mM (1.4 g / L). ) In a water bath at a temperature of 25 ° C. consisting of a mixed solution (concentration of zinc acetate is 20.9 g / L, concentration of manganese acetate is 0.2 g / L) mixed with 25 mL of an aqueous solution of manganese acetate. And soaking in an ultrasonic bath so that the residence time is 600 seconds in a 25 ° C. water bath composed of an aqueous sodium sulfide solution having a sodium sulfide concentration of 400 mM (31.2 g / L). did.
(3) Next, the PVA film was taken out from a water bath made of an aqueous sodium sulfide solution, and the taken out PVA film was added to an aqueous solution of zinc acetate to which manganese acetate was added in an amount of 1 mol% (the concentration of zinc acetate was 150 mM (27.5 g / L), a mixed solution (acetic acid) in which a zinc acetate aqueous solution having a manganese oxide concentration of 0.26 g / L) and a sodium sulfide aqueous solution having a sodium sulfide concentration of 150 mM (11.7 g / L) are mixed at a volume ratio of 1: 1. The zinc concentration was 13.75 g / L, the manganese acetate concentration was 0.13 g / L, and the sodium sulfide concentration was 5.85 g / L) (aging solution) (temperature 70 ° C.). Hold for 1 hour at ° C. Thereafter, the PVA film was taken out of the mixed solution, washed with water and methanol in this order, and dried with hot air at 50 ° C. to produce a PVA film containing zinc sulfide fine particles doped with manganese.

(4) The appearance of the PVA film obtained in the above (3) was smooth and good.
When the PVA film obtained in the above (3) was cut in the thickness direction and the cut surface was photographed with a transmission electron microscope (TEM), the phosphor fine particles were inside the PVA film as in FIG. As shown in FIG. 2, it was not adhered to the film surface when photographed with a scanning electron microscope (SEM). And when the average particle diameter of the phosphor fine particles (zinc sulfide fine particles) contained in the PVA film was determined by the above-described method based on the TEM photograph, it was 8 nm.
(5) Moreover, when the content of the phosphor fine particles and the activator (manganese) contained in the PVA film obtained in the above (3) was determined by the method described above, the content of the phosphor fine particles (including manganese) Was 1.39% by mass, and the doping rate of manganese as an activator was 0.63 mol% with respect to zinc element.

(6) Furthermore, when the light transmittance in the wavelength region of 200 to 800 nm (ultraviolet ray to visible light region) was measured for the PVA film obtained in (3) above, the wavelength region of 400 to 760 nm ( The average transmittance in the visible light region) is 96%, and the transmittance of visible light is high and the transparency is excellent. On the other hand, the transmittance of ultraviolet light having a wavelength of 300 nm is as low as 0.1% and the UV shielding property is excellent. It was.
(7) Further, when the PVA film obtained in (3) above was irradiated with an excitation wavelength (ultraviolet light) of 320 nm and its fluorescence spectrum was measured, as shown in FIG. Maximum absorption was observed.

Example 3
(1) In Example 2 (2), as an activator, an aqueous solution of copper acetate having a concentration of 8 mM (0.98 g / L) of copper acetate instead of an aqueous solution of manganese acetate having a concentration of 8 mM (1.38 g / L) of manganese acetate In (3), instead of the zinc acetate aqueous solution added with 1 mol% of manganese acetate, the zinc acetate aqueous solution added with 1.5 mol% of copper acetate (concentration of copper acetate is 0.28 g). Except for using / L.), The same operation as (1) to (3) of Example 2 was performed to manufacture a PVA film containing zinc sulfide fine particles doped with copper.
(2) The appearance of the PVA film obtained in (1) was smooth and good.
When the PVA film obtained in the above (1) was cut in the thickness direction and the cut surface was photographed with a transmission electron microscope (TEM), the phosphor fine particles were inside the PVA film as in FIG. As shown in FIG. 2, it was not adhered to the film surface when photographed with a scanning electron microscope (SEM). The average particle diameter of the phosphor fine particles (zinc sulfide fine particles) contained in the PVA film based on the TEM photograph was found to be 11 nm.
(3) Moreover, when the content of the phosphor fine particles and the activator (copper) contained in the PVA film obtained in the above (1) was determined by the method described above, the content of the phosphor fine particles (including copper) Was 1.10 mass%, and the doping ratio of copper as an activator was 1.36 mol% with respect to zinc element.

(4) Furthermore, when the light transmittance in the wavelength region of 200 to 800 nm (ultraviolet ray to visible light region) was measured for the PVA film obtained in (3) above, the wavelength region of 400 to 760 nm ( The average transmittance of visible light in the visible light region) is 92%, and the transmittance of visible light is high and the transparency is excellent. On the other hand, the transmittance of ultraviolet light having a wavelength of 300 nm is as low as 0.1%, and the ultraviolet light shielding. It was excellent in nature.
(5) When the PVA film obtained in (3) above was irradiated with an excitation wavelength (ultraviolet light) of 320 nm and its fluorescence spectrum was measured, as shown in FIG. Maximum absorption was observed.

Example 4
(1) A PVA film produced by adopting the same method as (1) of Example 1 is retained in a water bath at a temperature of 25 ° C. composed of an aqueous cadmium acetate solution having a cadmium acetate concentration of 150 mM (34.6 g / L). After dipping for 600 seconds, the residence time is 600 seconds in a 25 ° C. water bath composed of an aqueous sodium sulfide solution having a sodium sulfide concentration of 150 mM (11.7 g / L). Immersion under ultrasonic irradiation.
(2) Next, the PVA film was taken out of the water bath from the aqueous sodium sulfide solution, and the taken out PVA film was dissolved in a cadmium acetate aqueous solution having a cadmium acetate concentration of 150 mM (34.6 g / L) and a sodium sulfide concentration of 150 mM (11. 7 g / L) sodium sulfide aqueous solution mixed at a volume ratio of 1: 1 (cadmium acetate concentration is 17.3 g / L, sodium sulfide concentration is 5.85 g / L) (aging solution) ( Temperature) and kept at 70 ° C. for 1 hour. Thereafter, the PVA film was taken out of the mixed solution, washed with water and methanol in this order, and dried with hot air at 50 ° C. to produce a PVA film containing cadmium sulfide fine particles.

(3) The appearance of the PVA film obtained in (2) was smooth and good.
When the PVA film obtained in the above (2) was cut in the thickness direction and the cut surface was photographed with a transmission electron microscope (TEM), the phosphor fine particles were inside the PVA film as in FIG. As shown in FIG. 2, there was almost no adhesion to the surface of the film as photographed with a scanning electron microscope (SEM). And based on the said TEM photograph, it was 10 nm when the average particle diameter of the fluorescent substance fine particle (cadmium sulfide fine particle) contained in a PVA film was calculated | required by the above-mentioned method.
(4) Further, the content of the phosphor fine particles contained in the PVA film obtained in the above (2) was determined by the above-described method and found to be 1.50% by mass.

(5) Furthermore, when the light transmittance in the wavelength region of 200 to 800 nm (ultraviolet ray to visible light region) was measured for the PVA film obtained in (2) above, the wavelength region of 400 to 760 nm ( The average transmittance in the visible light region) is 61%, and although it is colored yellow, it is excellent in transparency, while the transmittance of ultraviolet light having a wavelength of 300 nm is as low as 0.1% and excellent in ultraviolet shielding properties. It was.
(6) When the PVA film obtained in (2) above was irradiated with an excitation wavelength (ultraviolet light) of 320 nm and its fluorescence spectrum was measured, a maximum absorption attributed to yellow fluorescence was observed near 550 nm. It was.

Example 5
(1) A PVA film produced by adopting the same method as (1) of Example 1 is retained in a water bath at a temperature of 25 ° C. composed of a zinc acetate aqueous solution having a zinc acetate concentration of 500 mM (91.8 g / L). Immerse so that the time is 600 seconds, and then ultrasonically adjust the residence time to 300 seconds in a 25 ° C. water bath composed of an aqueous sodium sulfide solution with a sodium sulfide concentration of 250 mM (19.5 g / L). After being immersed under irradiation, the PVA film was taken out from the aqueous sodium sulfide solution and washed with water.
(2) The above-mentioned series of steps (1) consisting of [immersion in a water bath composed of an aqueous zinc acetate solution-immersion in a water bath composed of an aqueous sodium sulfide solution-washing] was repeated four more times (total 5 times). .
(3) Next, the PVA film washed with water in the above (2) was subjected to a zinc acetate aqueous solution with a zinc acetate concentration of 500 mM (91.8 g / L) and sodium sulfide with a sodium sulfide concentration of 250 mM (19.5 g / L). Immersion in a mixed solution (concentration of zinc acetate is 45.9 g / L, concentration of sodium sulfide is 9.75 g / L) (aging solution) (temperature 70 ° C.) in which aqueous solution is mixed at a volume ratio of 1: 1 Then, after maintaining at 70 ° C. for 1 hour, the PVA film is taken out from the mixed solution, washed with water and methanol in this order, and dried with hot air at 50 ° C. to produce a PVA film containing zinc sulfide fine particles. did.

(4) The appearance of the PVA film obtained in the above (3) was smooth and good.
When the PVA film obtained in the above (3) was cut in the thickness direction and the cut surface was photographed with a transmission electron microscope (TEM), the phosphor fine particles were inside the PVA film as in FIG. As shown in FIG. 2, there was almost no adhesion to the surface of the film as photographed with a scanning electron microscope (SEM). And based on the said TEM photograph, it was 14 nm when the average particle diameter of the fluorescent substance fine particle (zinc sulfide fine particle) contained in a PVA film was calculated | required by the above-mentioned method.
(5) Further, the content of the phosphor fine particles contained in the PVA film obtained in the above (3) was determined by the above-described method and found to be 15.2% by mass.

(6) Furthermore, when the light transmittance in the wavelength region of 200 to 800 nm (ultraviolet ray to visible light region) was measured for the PVA film obtained in (3) above, the wavelength region of 400 to 760 nm ( The average transmittance in the visible light region) is 85%, and the visible light transmission is despite the phosphor fine particle content being about 5 to 10 times that of the PVA films obtained in Examples 1-4. The transmittance was high and the transparency was excellent. On the other hand, the transmittance of ultraviolet rays having a wavelength of 300 nm was as low as 0.1%, and the ultraviolet shielding properties were excellent.
(7) Further, when the fluorescence spectrum was measured by irradiating the PVA film obtained in (3) above with an excitation wavelength (ultraviolet rays) of 320 nm, a maximum absorption attributed to blue fluorescence was observed at around 430 nm. It was.

Example 6
(1) PVA (viscosity average polymerization degree = 1700, saponification degree = 99.8 mol%) was dissolved in water at 90 ° C. in a nitrogen atmosphere to prepare a spinning dope having a PVA concentration of 16% by mass. This spinning dope is wet-spun into a coagulation bath made of a saturated sodium sulfate aqueous solution through a nozzle having a hole diameter of 0.16 mm and a hole number of 108, and the resulting fiber is wet-drawn 5 times at 50 ° C. in water to obtain a PVA fiber ( A single fiber fineness of 30 dtex) was produced.
(2) The PVA fiber obtained in (1) above was prepared by using 150 mL of a zinc acetate aqueous solution with a zinc acetate concentration of 133 mM (24.4 g / L) and a manganese acetate (activator) concentration of 8 mM (1.4 g / L). ) In a water bath at a temperature of 25 ° C. consisting of a mixed solution (concentration of zinc acetate is 20.9 g / L, concentration of manganese acetate is 0.2 g / L) mixed with 25 mL of an aqueous solution of manganese acetate. And soaking in an ultrasonic bath so that the residence time is 600 seconds in a 25 ° C. water bath composed of an aqueous sodium sulfide solution having a sodium sulfide concentration of 400 mM (31.2 g / L). did.
(3) The series of steps (4) consisting of [immersion in a water bath comprising an aqueous solution containing zinc acetate and manganese acetate (activator) -immersion in a water bath comprising a sodium sulfide aqueous solution-washing with water] is further performed. Repeated 5 times (total 5 times).
(4) Next, the PVA fiber was taken out from the water bath made of an aqueous sodium sulfide solution, and the zinc acetate aqueous solution having a concentration of 150 mM (27.5 g / L) of zinc acetate to which manganese acetate was added in an amount of 1 mol% and sodium sulfide were added. A mixed solution in which a sodium sulfide aqueous solution having a concentration of 150 mM (11.7 g / L) is mixed at a volume ratio of 1: 1 (the concentration of zinc acetate is 13.75 g / L, the concentration of manganese acetate is 0.13 g / L, sulfide) The concentration of sodium was 5.85 g / L) (aging solution) (temperature 70 ° C.) and held at 70 ° C. for 1 hour. Then, the PVA fiber was taken out of the mixed solution and mixed with water and methanol. The PVA fiber containing zinc sulfide fine particles doped with manganese was manufactured by washing in order and drying with hot air at 50 ° C.

(5) The appearance of the PVA fiber obtained in the above (4) was smooth and good.
When the PVA fiber obtained in the above (4) was cut at right angles to the length direction and the cut surface was photographed with a transmission electron microscope (TEM), the phosphor fine particles were substantially contained inside the PVA fiber. It was uniformly dispersed, and when photographed with a scanning electron microscope (SEM), the phosphor fine particles were present only inside the PVA fibers and did not adhere to the fiber surface. And when the average particle diameter of the phosphor fine particles (zinc sulfide fine particles) contained in the PVA fiber was determined by the above-described method based on the TEM photograph, it was 18 nm.
(6) Moreover, when the content of the phosphor fine particles and the activator (manganese) contained in the PVA fiber obtained in the above (4) was determined by the method described above, the content of the phosphor fine particles (including manganese) Was 21.1% by mass, and the doping rate of manganese as an activator was 0.78 mol% with respect to zinc element.
(7) Further, when the fluorescence spectrum was measured by irradiating the PVA fiber obtained in (4) with an excitation wavelength (ultraviolet light) of 320 nm, a maximum absorption attributed to orange fluorescence was observed at around 580 nm. It was.

Example 7
(1) A PVA film containing zinc sulfide fine particles doped with manganese by performing the same operation as (1) and (2) of Example 2 except that the aging treatment of (3) of Example 2 was not performed. Manufactured.
(2) The appearance of the PVA film obtained in (1) was smooth and good.
When the PVA film obtained in the above (1) was cut in the thickness direction and the cut surface was photographed with a transmission electron microscope (TEM), the phosphor fine particles were inside the PVA film as in FIG. As shown in FIG. 2, it was not adhered to the film surface when photographed with a scanning electron microscope (SEM). And when the average particle diameter of the phosphor fine particles (zinc sulfide fine particles) contained in the PVA film was determined by the above method based on the TEM photograph, it was 9 nm.
(3) Moreover, when the content of the phosphor fine particles and the activator (manganese) contained in the PVA film obtained in the above (1) was determined by the method described above, the content of the phosphor fine particles (including manganese) Is 1.20 mass%, the doping rate of manganese as an activator is 0.32 mol% with respect to zinc element, and the content of the phosphor fine particles is found in Example 2 because no aging treatment was performed. The doping ratio of manganese as an activator was about half that of Example 2.

(4) Further, when the light transmittance in the wavelength range of 200 to 800 nm (ultraviolet ray to visible light range) was measured for the PVA film obtained in (1) above, the wavelength range of 400 to 760 nm ( The average transmittance in the visible light region) was 98%, and the visible light transmittance was high and transparent.
(5) Moreover, when the fluorescence spectrum was measured by irradiating the PVA film obtained in the above (1) with an excitation wavelength (ultraviolet light) of 320 nm, it was lower than the fluorescence intensity of Example 2 where the aging treatment was performed. A maximum absorption attributed to orange fluorescence was observed at around 580 nm.

<< Comparative Example 1 >>
(1) A zinc acetate aqueous solution having a zinc acetate concentration of 500 mM (91.8 g / L) and a sodium sulfide aqueous solution having a sodium sulfide concentration of 250 mM (19.5 g / L) were mixed at a volume ratio of 1: 1, A colloidal solution containing zinc sulfide fine particles was prepared.
(2) PVA (viscosity average polymerization degree = 1700, saponification degree = 99.9 mol%) was dissolved in water at 90 ° C. to prepare an aqueous solution having a PVA concentration of 10% by mass. Then, 0.3 parts by mass of the colloidal solution containing zinc sulfide particles prepared in the above (1) is mixed to prepare a mixed solution, which is cast on a metal at 60 ° C. and dried at 50 ° C. for 3 hours. A PVA film having a thickness of 75 μm was manufactured.

(3) The appearance of the PVA film obtained in the above (2) was clouded visually, and the presence of phosphor fine particles (zinc sulfide particles) was visually recognized under visible light.
The PVA film obtained in (2) above was cut in the thickness direction, and the cut surface was photographed with a transmission electron microscope (TEM) (FIG. 5). As shown in FIG. 5, in the obtained PVA film, the phosphor fine particles (zinc sulfide fine particles) were not dispersed on the order of several nanometers but were aggregated.
Based on the photograph of FIG. 5, when the average particle diameter of the phosphor fine particles (zinc sulfide fine particles) contained in the PVA film was determined by the method described above, it was 280 nm.
(4) Further, the content of the phosphor fine particles contained in the PVA film obtained in the above (2) was determined by the method described above, and was 2.70% by mass.

(5) Furthermore, when the light transmittance in the wavelength range of 200 to 800 nm (ultraviolet ray to visible light region) was measured for the PVA film obtained in (2) above, it was as shown in FIG. It was. From FIG. 3, when the average transmittance in the wavelength range of 400 to 760 nm (visible light range) and the transmittance of ultraviolet light having a wavelength of 300 nm were determined by the method described above, the transmittance of ultraviolet light having a wavelength of 300 nm was 0.1%. Although it was excellent in ultraviolet shielding property, the average visible light transmittance was 21%, the visible light transmittance was low, and the transparency was poor.
(6) When the PVA film obtained in (2) above was irradiated with an excitation wavelength (ultraviolet light) of 320 nm and its fluorescence spectrum was measured, a maximum absorption attributed to blue fluorescence was observed at around 430 nm. However, the visible light transmittance (transparency) was not excellent.

<< Comparative Example 2 >>
(1) A PVA film produced by adopting the same method as (1) of Example 1 is retained in a water bath at a temperature of 25 ° C. composed of a zinc acetate aqueous solution having a zinc acetate concentration of 20 mM (3.7 g / L). After dipping so that the time is 600 seconds, subsequently, the residence time is set to 300 seconds in a 25 ° C. water bath composed of an aqueous sodium sulfide solution having a sodium sulfide concentration of 10 mM (0.8 g / L). Immersion under ultrasonic irradiation.
(2) Next, the PVA film is taken out of the aqueous sodium sulfide solution from the water bath, and the aqueous zinc acetate concentration of 20 mM (3.7 g / L) and the sulfide concentration of 10 mM (0.8 g / L) of sodium sulfide are sulfided. In a mixed solution (concentration of zinc acetate: 1.85 g / L, concentration of sodium sulfide: 0.4 g / L) (maturation treatment solution) (temperature: 70 ° C.) in which sodium aqueous solution was mixed at a volume ratio of 1: 1 After dipping and holding at 70 ° C. for 1 hour, the PVA film is taken out of the mixed solution, washed with water and methanol in this order, and dried with hot air at 50 ° C. to obtain a PVA film containing zinc sulfide fine particles. Manufactured.

(3) The appearance of the PVA film obtained in (2) was smooth and good.
The PVA film obtained in the above (2) is cut in the thickness direction, and the cut surface is photographed with a transmission electron microscope (TEM). Based on the photograph, the phosphor fine particles contained in the PVA film It was 8 nm when the average particle diameter of (zinc sulfide fine particles) was determined by the above-described method.
(4) Further, the content of the phosphor fine particles contained in the PVA film obtained in the above (2) was determined by the method described above, and it was 0.31% by mass.
(5) Further, for the PVA film obtained in (2) above, when the light transmittance in the wavelength range of 200 to 800 nm (ultraviolet light to visible light region) was measured by the method described above, as shown in FIG. The average transmittance in the wavelength region of 400 to 760 nm (visible light region) was 99%, and the transmittance of visible light was high and excellent in transparency, but the transmittance of ultraviolet light at a wavelength of 300 nm was 29.4%. It was high and inferior in ultraviolet shielding properties.
(6) When the PVA film obtained in (2) above was irradiated with an excitation wavelength (ultraviolet light) of 320 nm and its fluorescence spectrum was measured, it was as shown in FIG. Fluorescence emission could not be confirmed visually.
A maximum absorption attributed to blue fluorescence was observed at around 430 nm.

<< Comparative Example 3 >>
(1) A commercially available nylon fiber (nylon 6 fiber, single fiber fineness 2 dtex) is prepared by adding 150 mL of a zinc acetate aqueous solution having a concentration of 133 mM (24.4 g / L) and a concentration of manganese acetate (activator) of 8 mM (1 4 g / L) of a mixed solution of 25 mL of an aqueous solution of manganese acetate (zinc acetate concentration is 20.9 g / L, manganese acetate concentration is 0.2 g / L). After dipping for 600 seconds, ultrasonic waves were applied so that the residence time was 600 seconds in a 25 ° C. water bath composed of a sodium sulfide aqueous solution having a concentration of sodium sulfide of 400 mM (31.2 g / L). Soaked under irradiation.
(2) Next, the nylon fiber is taken out from a water bath made of a sodium sulfide aqueous solution, and a zinc acetate aqueous solution having a concentration of 150 mM (27.5 g / L) of zinc acetate to which manganese acetate is added in an amount of 1 mol% is sulfided. A mixed solution in which a sodium sulfide aqueous solution having a sodium concentration of 150 mM (11.7 g / L) is mixed at a volume ratio of 1: 1 (the concentration of zinc acetate is 13.75 g / L, the concentration of manganese acetate is 0.13 g / L) The concentration of sodium sulfide is 5.85 g / L) (aging solution) (temperature 70 ° C.) and held at 70 ° C. for 1 hour, after which the nylon fiber is taken out of the mixed solution, They were washed with methanol in this order and dried with hot air at 50 ° C.

(3) When the contents of the phosphor fine particles and the activator (mann) contained in the nylon fiber obtained in (2) above are determined by the above-described method, the content of the phosphor fine particles (including manganese) is 0. 0.02 mass%, and the doping rate of manganese as an activator was 0.13 mol% with respect to zinc element.
Further, when the nylon fiber obtained in (2) was cut at right angles to the length direction and the cut surface was photographed with a transmission electron microscope (TEM), the phosphor fine particles inside the nylon fiber were photographed. The presence was not observed.
From the result of Comparative Example 3, even if the production method by dipping as in the present invention is applied to a polymer molded body having no hydroxyl group in the molecule such as nylon, phosphor fine particles are not formed in the molded body. It turns out that the molded object to disperse | distribute cannot be obtained.

  The results of Examples 1 to 7 and Comparative Examples 1 to 3 are summarized as shown in Table 1 below.

The fluorescent color-forming PVA resin molded article of the present invention has phosphor fine particles having an average particle diameter of 50 nm or less that emits clear and strong fluorescence under ultraviolet irradiation without the presence of the fine phosphor particles visible under visible light. In addition, since the phosphor fine particles are dispersed, the visible light transmittance is high and the transparency is excellent, the ultraviolet transmittance is low and the ultraviolet shielding property is excellent, and oxygen and other gases are also included. Fluorescence coloring changes due to surface adsorption, preventing counterfeiting of banknotes, securities, confidential documents, ID cards, product tags, etc., and UV shielding such as wallpaper, carpets, clothing, glass interlayer films, and glass adhesive films It can be effectively used for applications such as a material having decoration and a sensing material using gas surface adsorption.
And the above-mentioned fluorescence coloring PVA-type resin molding can be smoothly manufactured with the manufacturing method of this invention.

Claims (14)

  In the polyvinyl alcohol-based resin molded body, fluorescent fine particles having an average particle diameter of 50 nm or less that emit fluorescence in the wavelength range of 350 to 700 nm under irradiation of ultraviolet rays are formed of the polyvinyl alcohol-based polymer constituting the polyvinyl alcohol-based resin molded body. A fluorescent color-forming polyvinyl alcohol-based resin molded article which is contained in a state of being dispersed at a ratio of 0.5% by mass or more based on mass.   The fluorescent color-forming polyvinyl alcohol-based resin molded article according to claim 1, wherein the average particle diameter of the phosphor fine particles is 30 nm or less.   The phosphor fine particles are phosphor fine particles made of a metal compound (F) in which a group 16 element is bonded to a group 12 metal of the periodic table, which is doped or not doped with an activator. Fluorescent coloring polyvinyl alcohol resin molded product.   The phosphor fine particles are phosphor fine particles made of a metal compound (F) in which a group 16 element is bonded to a group 12 metal of the periodic table doped with an activator, and the amount of the activator The fluorescent coloring polyvinyl alcohol-based resin molded article according to any one of claims 1 to 3, wherein the amount is 0.001 mol or more with respect to 1 mol of the metal element of Group 12 of the periodic table before doping.   The phosphor fine particles are at least one kind of phosphor fine particles mainly composed of zinc sulfide doped or not doped with an activator and phosphor fine particles mainly composed of cadmium sulfide doped or not doped with an activator. The fluorescence coloring polyvinyl alcohol-type resin molding of any one of Claims 1-4.   The fluorescent color-forming polyvinyl alcohol-based resin molded body according to any one of claims 1 to 5, wherein the polyvinyl alcohol-based resin molded body is a film or a fiber.   The fluorescent color-forming polyvinyl alcohol-based resin molded article according to any one of claims 1 to 6, wherein the film has an average transmittance of visible light having a wavelength of 400 to 760 nm of 50% or more.   The fluorescent coloring polyvinyl alcohol-based resin molded article according to claim 7, wherein the film has a transmittance of ultraviolet rays having a wavelength of 300 nm of 10% or less. (I) A molded body made of a polyvinyl alcohol polymer is immersed in a liquid (Ia) containing a metal ion (A) that forms a metal compound (F) that emits fluorescence in a wavelength range of 350 to 700 nm under irradiation of ultraviolet rays. Or dipping in the liquid (Ib) containing the metal ion (A) and the activator ion (C);
(Ii) It is immersed in a liquid (II) containing ions (B) that react with the metal ions (A) to form a metal compound (F) that emits fluorescence in the wavelength region of 350 to 700 nm under irradiation of ultraviolet rays. Phosphor particles having an average particle diameter of 50 nm or less made of a metal compound (F) that emits fluorescence in a wavelength range of 350 to 700 nm under irradiation of ultraviolet rays are formed in a molded body made of a polyvinyl alcohol-based polymer;
(Iii) Immerse the molded body made of the polyvinyl alcohol polymer containing the phosphor fine particles formed in the step (ii) in the molded body in the liquid (IIIa) containing the metal ions (A) and ions (B). Or dipping in the liquid (IIIb) containing the metal ions (A), ions (B) and activator ions (C);
Production of a fluorescent color-forming polyvinyl alcohol-based resin molded article containing phosphor fine particles with an average particle diameter of 50 nm or less that are doped or not doped with an activator, characterized in that Method.   Liquid (Ia), liquid (Ib), liquid (II), liquid (IIIa), and liquid (IIIb) swell water, an organic solvent that swells the polyvinyl alcohol polymer, or water and the polyvinyl alcohol polymer. The production method according to claim 9, which is a liquid using a mixed solvent of organic solvents as a solvent. The production method according to claim 9 or 10, wherein the aging treatment in the step (iii) is performed at a temperature of 30 to 90 ° C for 30 minutes or more.   The content of the metal ion (A) generating compound in the liquid (Ia) and the liquid (Ib) is 0.1 to 120 g / L, and the content of the activator ion (C) generating compound in the liquid (Ib) is 0.1. 1 to 120 g / L, and the content of the ion (B) generating compound in the liquid (II) is 1 to 120 g / L (provided that the metal ion (A) generating compound in the liquid (Ia) and the liquid (Ib) And the content of the ion (B) generating compound in the liquid (II) is 5 g / L or more.), The metal ion (A) generating compound in the liquid (IIIa) and the liquid (IIIb) The content is 0.1 to 120 g / L and the content of the ion (B) generating compound is 0.1 to 120 g / L, and the content of the activator ion (C) generating compound in the liquid (IIIb) is 0.1. It is 1-120 g / L. The manufacturing method of any one of -11.   The manufacturing method according to any one of claims 9 to 12, wherein the metal ion (A) is an ion of a group 12 metal of the periodic table, and the ion (B) is an ion of an element of a group 16 of the periodic table.   The metal ion (A) is zinc ion or cadmium ion, the ion (B) is sulfur ion, and the activator ion (C) is at least one of manganese ion, copper ion, silver ion, gold ion and rare earth element ion The manufacturing method according to any one of claims 9 to 13.

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