KR100363720B1 - Invisible phosphorescent and fluorescent synthetic resin, its preparing and using method - Google Patents

Abstract

The present invention relates to an invisible dichroic phosphorescent and fluorescent synthetic resin, a manufacturing method and a method of using the same. More specifically, the present invention relates to a transparent thermoplastic resin or a thermosetting resin, wherein the transparent color or thermosetting resin is colorless and has different emission wavelengths and phosphors. It relates to an invisible dichroic phosphorescent and fluorescent synthetic resin comprising, a preparation method and a method of using the same. Invisible dichroic phosphorescent and fluorescent synthetic resins according to the present invention can be used in a variety of decorative products, clothing, danger indicators, toys, fashion products, as well as banknotes, bonds, passports, ID cards that require security It can be used as a functional element to prevent forgery or tampering in special products such as.

Description

Invisible dichroic phosphorescent and fluorescent synthetic resins, preparation method and using method thereof {Invisible phosphorescent and fluorescent synthetic resin, its preparing and using method}

The present invention relates to an invisible dichroic phosphorescent and fluorescent synthetic resin, a method of manufacturing and using the same, and more particularly to a transparent thermoplastic resin or a thermosetting resin, the appearance color is colorless and the emission wavelength is different, the external stimulus Invisible dichroic phosphorescent and fluorescent, which exhibits a fluorescent color when in an external stimulus, and a phosphorescent color after an external stimulus is removed by including a certain ratio of the phosphor that emits light when there is a light emitting substance after the external stimulus is removed. It relates to a synthetic resin, a preparation method thereof and a method of using the same.

Basically, the phenomenon of emitting the energy absorbed by the material as light is called luminescence, and it can be divided into phosphorescence and fluorescence. The difference between phosphorescence and fluorescence is generally classified as the difference in the time of emission by external stimulation. In the case of fluorescence, the emission time after the excitation is stopped is 10 ^-4 (sec) or less, and the phosphorescence is longer than the emission time. It is generally classified as having.

In addition, phosphorescence and fluorescence are substances that emit light toward longer wavelengths by being excited by absorbed light, and are classified into inorganic fluorescence and daylight fluorescence. Inorganic fluorescence has the property of phosphorescence in which the excited state remains even after being stimulated by light, and the pigment having this property is used for the luminous paint, and the phosphorescent pigment is composed of a self-luminous pigment having self-luminescence properties by half-radiation of radioactive elements. Phosphorescent light in the present invention encompasses the concept of self-luminous and phosphorescent pigments.

The phosphors used in the prior art were mainly sulfide-based, and the phosphors and luminescent properties showed that CaS: Bi was a violet emission, CaSrS: Bi was a blue emission, ZnS: Cu was a green emission, and ZnSCdS: Cu was a yellow color. Light emission and the like. Such sulfide-based phosphors are chemically unstable and poor in light resistance, and thus have many problems in practical terms, but are used in part due to their low price. Particularly, ZnS: Cu phosphors are limited to luminous clocks, danger lights, and emergency signs because they are photodegraded by ultraviolet rays and turn black when moisture is present.

Recently, phosphorescence of MAl ₂ O ₄ system (where M is Ca, Sr, Ba and Mg), YAlO ₃ : Ce ³⁺ (green light emission), chemically stable, excellent light resistance, long afterglow and strong luminous intensity Materials have been developed and put into practical use.

In addition, the fluorescent material used in the prior art is quite diverse, mainly organic fluorescent dyes or pigments are used, the pigment type thereof is a lumogen color (Lumogen Color) is commonly used, and a synthetic resin solid solution type is obtained by dispersing dyes such as di and triphenylmethane, chianthene, thiazole and thiazine based on synthetic resins such as melamine resin, urea resin, and sulfonamide resin. . These fluorescent pigments are mostly fine particles by dispersing the fluorescent dye in a specific resin, because in order for the fluorescent dye to emit fluorescence with high efficiency, the individual molecules must be dispersed in such a thin state that they do not affect each other. To this end, by using a method of insolubilizing by mixing in the resin has an effect that the fluorescence intensity is increased and the light resistance is improved. Fluorescent pigments currently on the market are generally manufactured by dispersing in thermoplastic resins such as acrylic resins, polyester resins, polyamide resins, or by mixing them with thermosetting resins.

Recently, Sr (PO ₂ ) Cl: Eu (blue light emission), Zn ₂ GeO ₂ : Mn (green light emission), Y ₂ O ₂ S: Eu (red light emission) metal Compounds are being used for development.

Synthetic resin products having the conventional phosphorescent properties can be printed or applied by dispersing the phosphorescent pigment in any synthetic resin and producing a fiber or sheet by injection, or by manufacturing a phosphorescent pigment on the resin surface of the fiber or sheet as a paint or ink. And a coating method, and related documents thereof include Korean Patent Registration No. 087861 (1998) and Japanese Patent Laid-Open No. 6-33312 (1994) and Japanese Patent Laid-Open No. 8-127937 (1996). It describes a photoluminescent synthetic resin in which a metal oxide phosphor is dispersed in a synthetic resin.

Synthetic resin products having the above-mentioned phosphorescent properties exhibit a certain visible light even after irradiating or removing ultraviolet rays, and thus are widely used in decorative products, clothing, danger indicators, toys, and fashion products. In addition, it accumulates the energy of visible light and continuously emits light for a specific time even in the dark.

In addition, a conventional synthetic resin product having a fluorescence property is prepared by melting or dispersing a fluorescent pigment or fluorescent dye having a colorless or colored external color in any synthetic resin, and made into a fiber or sheet by injection, or a fluorescent dye on the resin surface of the fiber or sheet It is prepared by using a method of fixing, or printing, applying and coating fluorescent pigments or fluorescent dyes with a paint or ink. Related documents include Japanese Patent Application Laid-Open No. 63-196719 (1988), Japanese Patent Application Laid-Open No. 63-165517 (1988), and Japanese Patent Application Laid-Open No. 2-200811 (1990). Fluorescent synthetic resins prepared by dispersing are described.

However, since synthetic resin products having fluorescence properties are used in decorative products, clothing, lighting, danger indicators, toys, and fashion products because they display specific visible light under ultraviolet light, they emit light only when irradiated with ultraviolet light and remove ultraviolet light. When the light emission phenomenon disappears immediately.

In addition, U.S. Patent No. 5,498,280 describes a technique for preparing a crayon for marking in which a fluorescent and phosphorescent pigment is combined with polyethylene glycol and a wax. However, the present invention does not have a dichroic emission concept and cannot be manufactured from plastic films or fibers. In addition, Japanese Patent Application Laid-open No. Hei 10-168441 describes a method of using a combination of colored pigments, such as a luminescent wavelength of phosphorescent pigments, and Japanese Patent Laid-Open No. 11-158420 by coloring the surface of the phosphorescent pigment with a colored material When copying color, color pigments can be reproduced but used as a copy protection material that cannot reproduce the phosphorescence effect. On the other hand, Japanese Patent Application Laid-Open No. 9-208774 discloses a PVC adhesive tape combining a PVC resin with fluorescent and phosphorescent pigments. However, the appearance color is colored and PVC resin has a problem of emitting toxic components such as dioxins when the fiber spinning properties are poor and when burned with a toxic plasticizer. In addition, since the appearance is colored, not only the color is mixed at the time of color development by fluorescence and photoluminescence, but also affects the color development of the photoluminescent pigment, thereby lowering the effect.

As described above, the conventional resin having phosphorescence and fluorescence properties is composed of only fluorescence or phosphorescence alone as described above, and thus has monochromatic defects, that is, monochromatic luminescence properties of one color, or is used in combination with colored pigments. Thereby only concealed phosphorescent effect.

The present inventors have studied and researched to solve these drawbacks, considering that the synthetic resin of phosphorescent properties and fluorescent resins were separately used and that synthetic resins considering invisible dichroic emission characteristics were not examined. A light emitting resin containing two characteristics was developed and the present invention was completed based on this.

Accordingly, an object of the present invention is to solve the conventional problems and use a fluorescent material and a phosphor that are colorless in appearance color and have different emission wavelengths, respectively, and exhibit fluorescence emission color at the time of external stimulation such as ultraviolet irradiation and after the external stimulus is removed. The present invention provides invisible dichroic phosphorescent and fluorescent synthetic resins which are combined so that phosphorescent colors appear differently.

It is another object of the present invention to provide a method for preparing the invisible dichroic phosphorescent and fluorescent synthetic resins.

Still another object of the present invention is to provide a method of using the invisible dichroic phosphorescent and fluorescent synthetic resins.

In order to achieve the above object, the invisible dichroic phosphorescent and fluorescent synthetic resins of the present invention have a colorless or almost no color in appearance and are 0.001 to 20% by weight of a fluorescent substance emitting light when there is an external stimulus. It consists of 3 to 50% by weight of the phosphor and a light emitting material different from the fluorescent material and emitting light after the external stimulus is removed, and the remaining thermoplastic resin or thermosetting resin.

Method for producing a non-visible dichroic phosphorescent and fluorescent synthetic resin of the present invention for achieving another object, 0.001 to 20% by weight of the fluorescent material emitting light when the external color is colorless or almost no color, the external stimulation, the external color It is made of colorless or colorless and is made by mixing and stirring 3 to 50% by weight of the phosphor and the remaining thermoplastic resin or thermosetting resin which are different from the fluorescent material and have a different wavelength of light emission and are removed after external stimulation.

The method of using the invisible dichroic phosphorescent and fluorescent synthetic resin of the present invention to achieve another object is to manufacture the invisible dichroic phosphorescent and fluorescent synthetic resin according to the invention as a fiber or sheet to decorate, clothing, risk It consists of gifts, hidden wires and security elements for forgery and tampering of labels, toys, fashion products and special products requiring security.

Hereinafter, the present invention will be described in detail.

As described above, the present invention relates to an invisible dichroic phosphorescent and fluorescent synthetic resin which is excited by an external stimulus to represent a fluorescent color of a fluorescent material and a phosphorescent color due to a phosphor in a dark place where the external stimulus is removed. The resin used in the invention is preferably a resin having a melting point that is lower than the decomposition or decomposition temperature of the phosphor or fluorescent substance, and is, for example, single or mixed of polystyrene, polycarbonate, polyamide, polyester, polyolefin, polyvinyl alcohol, and the like. Thermoplastic resins may be used, and when used as a molded product, thermosetting resins such as phenol, melamine, epoxy, and urethane resins may also be used.

In addition, the fluorescent material used in the present invention can be used both organic and inorganic color of the external color is almost colorless or almost no color, the phosphor and the emission wavelength used together is different, in the case of organic type can also use dyes and the external color It is effective to have a colorless or pale color which is invisible for a unique emission color. Examples of the phosphor include organic light emitting coumarins, yellow light emitting oxazinones, and the like. Inorganic light emitting devices include blue light emitting Sr (PO ₂ ) Cl: Eu, green light emitting Zn ₂ GeO ₂ : Mn, and red light emitting light. Y ₂ O ₂ S: Eu-based, green light-emitting BaMgAl: (Eu, Mn) -based, red-emitting Y ₂ O ₃ : Eu and the like, it is also effective to use a colorless phosphorescent pigment with a short afterglow time. The amount of the fluorescent substance used is 0.001 to 20% by weight, and since the particles of the fluorescent substance are generally sufficiently small, they do not have a great influence in manufacturing products such as fibers, sheets, and moldings, but the content of the fluorescent substance contained in the resin is It has an important influence on molding into the product. Here, if the content is less than 0.001% by weight, there is a problem that the fluorescence effect is lowered, and when the content exceeds 20% by weight, the molding condition worsens and the fluorescence is quenched.

If the fluorescent material is in the form of a pigment in the synthetic resin, it is easy to disperse it by simple stirring and fleshing, but in the case of the dye, it is difficult to disperse the resin and the dye at the same time because the content is small in the synthetic resin is small. It can be selected and uniformly dispersed and then used to remove the solvent. Such solvents may vary depending on the components of the fluorescent material, but are generally aromatic solvents such as benzene and toluene, ketone solvents such as acetone and methyl ethyl ketone, and dimethyl. Formamide, chloroform, acetonitrile and the like.

The phosphor used in the present invention is in the form of a metal compound or metal oxide having a different light emission wavelength from the fluorescent material, and the exterior color is invisibly colorless or pale in color for a unique light emission color like the fluorescent material. It is desirable that afterglow can last for several seconds or more in the dark even after the stimulus has been removed. Such phosphors include ZnS: Cu of green luminescence, SrS: Eu of red luminescence of slightly yellowish appearance, SrCaS: Bi of blue luminescence, YAlO ₃ : Ce of green luminescence, and MAl ₂ O having various emission colors according to metal types. ₄ systems (where M is Ca, Sr, Ba, Mg), etc. are mentioned.

Phosphors used in the present invention (phosphor) are mostly composed of metal oxides and metal compounds, so they have a certain particle size, the phosphor is a large particle in terms of physical properties is high luminescence performance, but if the particle size is large fiber, thin film sheet , It has a bad effect on making products such as fine moldings, and synthetic resins containing phosphors decrease the radioactivity, elongation, flexibility, etc. during molding. It is desirable to have a particle diameter corresponding to 1/3 or less of the fiber diameter, and when made of sheets and other moldings, 1/2 or less of the product diameter is preferable.

In addition, the content of the phosphor contained in the synthetic resin also has an important effect on the molding of the product, the amount of the use is 3 to 50% by weight, the content is less than 3% by weight there is a problem that the phosphorescent effect is lowered, more than 50% by weight If the molding condition worsens. Usually, 3 to 30 weight% is preferable when manufacturing with a fiber yarn, and 3 to 50 weight% is preferable when manufacturing with a sheet | seat and other moldings.

As a method of mixing the resin, the fluorescent material and the phosphor as described above, there are three main methods, firstly, the method of stirring the fluorescent material and the phosphor material into the synthetic resin at the same time, and secondly, independent of the fluorescent material and the phosphor material. And then mixing the resin with the resin, and dissolving the third useful soluble substance in a solvent alone or with a resin that acts as a binder of the fluorescent substance, and depositing phosphor particles of fine particles having a certain size in the solution. When the solvent is evaporated, the fluorescent material is coated on the surface of the phosphor to prepare a phosphor having a combination of phosphorescence and fluorescence, and a method of dispersing and mixing the phosphor in the synthetic resin.

The first method may be used when both the fluorescent material and the phosphor are homogeneous in the form of pigments, and by mixing and stirring the two pigments in a predetermined ratio in the synthetic resin, the product may be completed.

The second method can also be used when the phosphor and the phosphor are heterogeneous, e.g. when it is difficult to uniformly disperse in the resin, such as when the phosphor is in the form of a useful dye and the phosphor is in the form of a pigment. The product may be completed by mixing and stirring the resin independently and then mixing and injecting the two resins in a subsequent process, or resins containing phosphors and resins containing phosphors may be prepared as fibers or sheets, respectively. After manufacture, it can be spliced or glued to complete the product. In this case, when the phosphorescent mixed resin is manufactured, the surface of the phosphorescent pigment may be contaminated by the soft material or the particles may become small due to the softening method. Therefore, the phosphorescent mixed resin may be mixed using a stirring method.

In the third method, the oil-soluble fluorescent substance is dissolved in a solvent alone or together with a resin serving as a binder of the fluorescent substance, and then, the solution is deposited by depositing the fine particles having a certain size and then evaporated. A phosphor is coated on the surface to prepare a phosphor having a combination of phosphorescence and fluorescence properties, and the phosphor is preferably prepared by dispersing 4 to 50% by weight of the phosphor or 50 to 96% by weight of the thermosetting resin. . The usable solvents may vary depending on the components of the fluorescent material as described above, but generally include aromatic solvents such as benzene and toluene, ketone solvents such as acetone and methyl ethyl ketone, and dimethylformamide, chloroform, acetonitrile, and the like. Can be mentioned.

In the present invention, in order to obtain products such as fibers, sheets, and moldings having desired phosphorescence and fluorescence properties, the composition ratio of the fluorescent substance, the phosphor, and the synthetic resin is important. For the unique light emission color, the phosphor and the phosphor are almost colorless. It is preferable to use them combining suitably so that each may have a different light emission wavelength.

In the present invention, the distinction between phosphorescence and fluorescence is not limited to 10 ^-4 (sec), which is a conventional light emission time, but is intended to limit the light emission time to 1 second or more. A part of the phosphor that is 1 second or less was classified as a phosphor.

Hereinafter, the present invention will be described in more detail, but the scope of the present invention is not limited thereto.

Example 1

Al ₂ O ₃ : Sr phosphorescent pigments (color: nylon 6, colorless, melting point: 250 ° C), colorless and yellowish green. (Manufacturer: Uksung Chemical, product name: PANAX LUMINO GREEN, green emission wavelength) : 15 wt% of 520 nm, particles: 3 μm on average, 1 wt% of polyaromatic fluorescent pigment (manufacturer: Uksung Chemical, trade name: PANAX RED PKS-225, emission color: red emission wavelength: 611 nm) The fiber was spun to have a diameter of about 30 μm (about 9 denier). The appearance color of this fiber is milky white by phosphorescent and fluorescent pigments. When ultraviolet rays are irradiated in a dark place, red light is emitted by fluorescent pigments, and yellow green light is emitted by phosphorescent pigments when ultraviolet light is removed.

Example 2

Al ₂ O ₃ : Sr phosphorescent pigments (color: nylon 6, colorless, melting point: 250 ° C), colorless and yellowish green. (Manufacturer: Uksung Chemical, product name: PANAX LUMINO GREEN, green emission wavelength) : 520 nm, particles: an average of 3 μm) was added to 15% by weight to stir and disperse to prepare a phosphorescent synthetic resin, and to melt polyamide (nylon 6, colorless, melting point: 250 ℃) polyaromatic fluorescent pigment ( Manufacturer: Uksung Chemical, trade name: PANAX RED PKS-225, emission color: red light emission wavelength: 611nm) by adding 1% by weight to disperse to prepare a fluorescent synthetic resin, each of the phosphorescent and fluorescent resin by mixing 50% by weight It was melted and spun to have a fiber diameter of about 30 μm (about 9 denier). Some were injected into sheets to have a thickness of about 0.1 mm. Appearance, phosphorescence and fluorescent color were the same as in Example 1, the fluorescent pigment was uniformly dispersed, the effect was excellent with the fluorescence emission.

Example 3

A phosphor prepared by spinning the phosphorescent synthetic resin and the fluorescent synthetic resin of Example 2 to form a fiber or sheet, and then mixed in a ratio of 1: 1 to prepare a fiber. This was also excellent in the dichroic luminous effect of phosphorescence and fluorescence.

Example 4

In 50 ml of dimethylformamide (DMF), 1 g of PANAX RED PKS-225 fluorescent pigment and 5 g of vinyl chloride resin are dissolved. When 30 g of phosphorescent pigment was added thereto and the solvent was removed under reduced pressure while stirring, a phosphorescent pigment with a uniform coating of fluorescent pigment on the surface of the phosphor was prepared. 80 wt% of the melted polyamide (nylon 6, colorless, melting point: 250 ° C.) was added thereto and 20 wt% was melted to spin to a diameter of about 30 μm (about 9 denier) and sheeted to a desired thickness. Appearance, phosphorescence and fluorescent colors were the same as in Example 1, because the fluorescent pigment is uniformly coated on the phosphorescent pigment, it was excellent in the dichroic emission effect of phosphorescence and fluorescence.

As can be seen through the above embodiment, the product according to the present invention has a colorless appearance or almost no color, and includes both a phosphor and a fluorescent material having different emission wavelengths, and thus external stimulation such as ultraviolet irradiation. In the case of fluorescence emission color, and when the external stimulus is removed, the phosphorescence emission color is obtained, thereby obtaining a material having a dichroic luminescence effect having no mixed color at all. Invisible dichroic phosphorescent and fluorescent synthetic resin products having both phosphorescent and fluorescent effects are not only widely used in decorative products, clothing, hazard indicators, toys and fashion products, but also for special products requiring banking security (banknotes, certificates). When applied to bonds, passports, identification cards, etc., it can be used as a functional element to prevent forgery or tampering.

Claims (13)

Outer color is almost colorless or colorless and emits light when there is an external stimulus 0.001 to 20% by weight, outward color is almost colorless or colorless, the luminescent wavelength is different from the fluorescent material and is emitted after the external stimulus is removed 3 to 50% by weight of the phosphor and the remainder of the thermoplastic resin or thermosetting resin, wherein the fluorescent material is organic blue light coumarin-based, yellow light-emitting oxazinone-based, inorganic blue light-emitting Sr (PO ₂ ) Cl: Eu , Green light-emitting Zn ₂ GeO ₂ : Mn, red light-emitting Y ₂ O ₂ S: Eu, green light-emitting BaMgAl: (Eu, Mn) -based, red light-emitting Y ₂ O ₃ : Eu, afterglow time At least one is selected from the group consisting of short colorless phosphorescent pigments, and the phosphors are ZnS: Cu of green luminescence, SrS: Eu of red luminescence with slightly yellow appearance, SrCaS: Bi of blue luminescence, YAlO ₃ of green luminescence : MAl ₂ with various emission colors depending on Ce and metal An invisible dichroic phosphorescent and fluorescent synthetic resin, characterized in that the O ₄ system (wherein M is Ca, Sr, Ba, Mg) at least one selected from the group consisting of metal compounds or metal oxides. delete delete Outer color is almost colorless or colorless and emits light when there is an external stimulus 0.001 to 20% by weight, outward color is almost colorless or colorless, the luminescent wavelength is different from the fluorescent material and is emitted after the external stimulus is removed It is prepared by mixing and stirring 3 to 50% by weight of the phosphor and the rest of the thermoplastic or thermosetting resin, the fluorescent material is organic blue light coumarin-based, yellow light-emitting oxazinone-based, inorganic blue light-emitting Sr (PO ₂ ) Cl: Eu, green light-emitting Zn ₂ GeO ₂ : Mn, red light-emitting Y ₂ O ₂ S: Eu system, green light-emitting BaMgAl: (Eu, Mn) system, and red light-emitting Y ₂ O ₃ : Eu system, At least one selected from the group consisting of colorless phosphorescent pigments having a short afterglow time, and the phosphor material is ZnS: Cu of green light emission, SrS: Eu of red light emission of slightly yellow appearance, SrCaS: Bi of blue light emission, green light emission of YAlO _3: Ce and a variety of foot, depending on the type of metal MAl having a color ₂ O ₄ based on non-visible dichroic phosphorescent and fluorescent synthetic resin with a metal compound or a metal oxide, characterized in that (wherein, M represents Ca, Sr, Ba, Mg) is at least one selected from guneu consisting of Manufacturing method. delete delete The invisible dichroic phosphorescent compound according to claim 4, wherein when the fluorescent substance and the phosphor are all homogeneous in the form of a pigment, a mixture of a thermoplastic resin or a thermosetting resin, a fluorescent substance, and a phosphor is mixed and stirred together. And a method of preparing a fluorescent synthetic resin. The method of claim 4, wherein when the fluorescent material and the phosphor are heterogeneous, the fluorescent material is mixed and stirred with a thermoplastic resin or a thermosetting resin, and the phosphor and the phosphor are contained after mixing and stirring the phosphor material independently with the resin. Method for producing a non-visible dichroic phosphorescent and fluorescent synthetic resin characterized in that the prepared resin is mixed and stirred. The method of claim 4, wherein when the fluorescent material and the phosphor are heterogeneous, after mixing and stirring the fluorescent material with a thermoplastic resin or a thermosetting resin, and independently mixing and stirring the phosphor with the resin, A method for producing an invisible dichroic phosphorescent and fluorescent synthetic resin, characterized in that the resin is produced by fiber or sheet and then manufactured by plywood or adhesion. The phosphor is prepared by combining phosphorescent and fluorescent properties by dissolving the phosphor in a solvent, depositing a phosphor in the solution, and then evaporating the solvent to prepare a phosphor having a combination of phosphorescence and fluorescence properties. A method for producing an invisible dichroic phosphorescent and fluorescent synthetic resin, characterized in that it is prepared by dispersing% in 50 to 96% by weight of the thermoplastic resin or thermosetting resin. The invisible dichroic phosphorescent and fluorescent synthetic resin according to claim 1 made of fiber or sheet, decorative articles, clothing, risk indicators, toys, fashion products, gifts for banknotes, bonds, passports or ID cards for counterfeiting and tampering; Method of using invisible dichroic phosphorescent and fluorescent synthetic resin, characterized in that it is used as a hidden line and a security element. delete The method of claim 1, wherein the thermoplastic resin is selected from the group consisting of polystyrene, polycarbonate, polyamide, polyester, polyolefin, polyvinyl alcohol and mixtures thereof, and the thermosetting resin is a phenol, melamine, epoxy and urethane resin. Invisible dichroic phosphorescent and fluorescent synthetic resin, characterized in that selected from the group consisting of.