JP3710513B2 - Fluorescent printing material, fluorescent printed matter, and fluorescent printing method - Google Patents

Description

[0001]
[Industrial application fields]
The present invention relates to a fluorescent printing material, a method for producing a fluorescent printed material, and a fluorescent printed material. More specifically, when printing a fluorescent barcode or the like using an ink containing a fluorescent dye, the fluorescent intensity of the formed fluorescent printing is not reduced or hardly reduced, The present invention relates to a manufacturing method and a fluorescent printed material.
[0002]
[Prior art]
The fluorescent printed matter has a fluorescent printed layer that cannot be substantially recognized with the naked eye, but becomes readable by being irradiated with ultraviolet rays.
For example, when the fluorescent printing layer is a barcode, it cannot be recognized with the naked eye, but the barcode information can be read and confirmed as necessary. Such invisible (invisible) barcodes are considered to be effective as anti-counterfeiting means such as printed securities, traffic coupons, commuter passes, and the like.
[0003]
An invisible printing layer such as an invisible barcode is also useful as a means for recording necessary information without impairing the appearance of the original printing layer. For example, by providing an invisible print layer on the surface of a CD-ROM or LD, information can be given for searching without impairing the appearance.
[0004]
[Problems to be solved by the invention]
By the way, it has been proposed that a fluorescent print is provided with an ultraviolet absorbing layer as a back coat layer directly under the fluorescent print layer in order to keep the fluorescence emission intensity from the fluorescent print constant [WO92 / 20748]. In particular, in the case of the above invisible barcode, if the intensity of the fluorescent light emitted from the barcode is not uniform, the barcode information may not be read correctly.
[0005]
However, when the present inventors conducted a formation test of various fluorescent printing layers on the material having the ultraviolet absorbing layer as described above, when an ink containing a fluorescent dye is used as the fluorescent ink, it is compared with the original strength. Only half the fluorescence intensity was obtained.
The fluorescent substances contained in the fluorescent ink can be roughly classified into fluorescent dyes and fluorescent pigments. A fluorescent pigment has low light emission intensity but excellent light resistance. On the other hand, fluorescent dyes are characterized by low light resistance but high emission intensity. Therefore, when a high emission intensity is desired, a fluorescent dye is generally used. However, the problem of a decrease in the fluorescence intensity as described above has been revealed for the first time.
[0006]
Accordingly, an object of the present invention is a material having an ultraviolet absorbing layer as a backcoat layer, and even when a fluorescent printing layer is formed using an ink containing a fluorescent dye, the fluorescence intensity of the formed fluorescent printing layer is reduced. An object of the present invention is to provide a fluorescent printing material capable of preventing the above-described problem.
Furthermore, an object of the present invention is a printing method for forming a fluorescent printing layer using an ink containing a fluorescent dye on a material having an ultraviolet absorbing layer as a backcoat layer, and reducing the fluorescence intensity of the formed fluorescent printing layer It is an object of the present invention to provide a method for producing a fluorescent printed material that can prevent the above-described problem.
In addition, an object of the present invention is to have an ultraviolet absorbing layer as a backcoat layer and a fluorescent printing layer formed with an ink containing a fluorescent dye thereon, and the fluorescent intensity of the fluorescent printing layer maintains its original intensity. It is to provide a fluorescent print.
[0007]
[Means for Solving the Problems]
The present invention is a printing material using an ink containing a fluorescent dye, and has a UV absorbing layer on a substrate, and the UV absorber is substantially fixed in the UV absorbing layer. And a fluorescent printing material (hereinafter referred to as a fluorescent printing material of the first aspect).
[0008]
Furthermore, the present invention provides a method for producing a fluorescent printed material (hereinafter referred to as the production method of the first aspect), wherein an ink containing a fluorescent dye is printed on the ultraviolet absorbing layer of the fluorescent printing material of the present invention. About.
[0009]
The present invention is also a printing material using an ink containing a fluorescent dye, having a UV absorbing layer on the substrate, and substantially transparent to UV and visible light on the UV absorbing layer. A fluorescent printing material characterized in that the protective layer is substantially impermeable to the fluorescent dye in the ink and the ultraviolet absorbent in the ultraviolet absorbing layer (hereinafter referred to as a fluorescent printing material). The fluorescent printing material of the second aspect).
[0010]
In addition, the present invention provides a method for producing a fluorescent printed matter (hereinafter, referred to as a production method of the second aspect), wherein an ink containing a fluorescent dye is printed on the protective layer of the fluorescent printing material of the present invention. About.
[0011]
Furthermore, the present invention is a printed matter having a printed layer formed of an ink containing a fluorescent dye on an ultraviolet absorbing layer on a substrate, wherein the ultraviolet absorbent is substantially fixed in the ultraviolet absorbing layer. The present invention relates to a fluorescent printed matter (hereinafter referred to as a fluorescent printed matter of the first aspect).
[0012]
Further, the present invention comprises, in this order, an ultraviolet absorbing layer, a protective layer substantially transparent to ultraviolet rays and visible light, and a printed layer formed of an ink containing a fluorescent dye on the substrate, and The protective layer is substantially impermeable to the fluorescent dye in the ink and the ultraviolet absorbent in the ultraviolet absorbing layer, and relates to a fluorescent printed material (hereinafter referred to as the fluorescent printed material of the second aspect). .
[0013]
In addition, the present invention relates to a fluorescent barcode reading method, wherein the barcode of the fluorescent printed matter of the present invention is read using a light source having a wavelength in the range of 200 to 350 nm.
The present invention will be described below.
[0014]
The fluorescent printing material according to the first aspect of the present invention comprises at least a base material and an ultraviolet absorbing layer.
Examples of the substrate include a resin film and paper. Examples of the resin film include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyethylene oxide, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyether, polyester, polyethylene terephthalate, nylon, cellulose acetate, ethyl cellulose, and cellulose nitrate. And resin films such as propylcellulose. High-grade printing paper, intermediate printing paper, low-grade printing paper, coated paper, lightweight coated paper, cast coated paper (mirror coated paper), embossed paper, art post paper, art paper, thin leaf printing paper, fine coating printing Examples include paper, brightener-containing paper, paraffin paper, resin-impregnated paper, synthetic paper, fancy coated paper, pure white roll-coated paper, colored fine paper, fluorescent paper, special printing paper (such as a postcard made by a government agency).
[0015]
Moreover, the ultraviolet absorber is substantially fixed in the ultraviolet absorbing layer. Further, the ultraviolet absorbing layer is substantially transparent to visible light. The fixing of the ultraviolet absorbent to the ultraviolet absorbing layer means that the ultraviolet absorbent does not substantially move to the fluorescent printing layer even if the fluorescent printing layer is formed directly on the ultraviolet absorbing layer. For example, the ultraviolet absorbing layer can be composed of at least an ultraviolet absorbent and a resin, and the ultraviolet absorbent can be selected from the group consisting of particulates having ultraviolet absorbing ability or resin having an ultraviolet absorbing functional group. An ultraviolet absorbing layer in which the absorbent is substantially fixed can be formed.
[0016]
The particulate matter having ultraviolet absorbing ability is, for example, an ultraviolet absorbing inorganic pigment, and examples of the ultraviolet absorbing inorganic pigment include zinc oxide and titanium oxide. From the viewpoint that these particulate matters are substantially transparent to visible light and do not substantially move to the fluorescent printing layer, it is appropriate that the particle diameter is in the range of 0.01 to 1 μm.
[0017]
The resin having an ultraviolet absorbing functional group can be, for example, a resin in which an ultraviolet absorber such as tinuvin is chemically bonded to the resin. As an example of such a resin, for example, emulsion Tinuvin (manufactured by Ciba Geigy) and the like can be mentioned.
[0018]
As the resin that serves as a vehicle component for forming the ultraviolet absorbing layer, a resin that is substantially transparent to visible light is used. Examples of such resins include polyethylene-based [polyethylene (PE), ethylene-vinyl acetate copolymer (EVA), vinyl chloride-vinyl acetate copolymer], polypropylene (PP), vinyl-based [polyvinyl chloride ( PVC), polyvinyl butyral (PVB), polyvinyl alcohol (PVA), polyvinylidene chloride (PVdC), polyvinyl acetate (PVAc), polyvinyl formal (PVF)], polystyrene [polystyrene (PS), styrene-acrylonitrile copolymer (AS), ABS], acrylic [polymethyl methacrylate (PMMA), MMA-styrene copolymer], polycarbonate (PC), cellulose [ethyl cellulose (EC), cellulose acetate (CA), propyl cellulose (CP), Acetic acid / butyric acid cellulose (CAB), cellulose nitrate (CN), fluorine-based [polychlorofluoroethylene (PCTFE), polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoroethylene copolymer (FEP), polyvinylidene fluoride (PVdF) )], Urethane (PU), nylon [type 6, type 66, type 610, type 11], polyester [polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycyclohexane terephthalate (PCT), etc. A plastic resin can be mentioned.
[0019]
Furthermore, these resins can be emulsions for aqueous paints. Examples of emulsions for water-based paints include vinyl acetate (homo) emulsion, vinyl acetate-acrylate copolymer resin emulsion, vinyl acetate-ethylene copolymer resin emulsion (EVA emulsion), and vinyl acetate-vinyl versateton copolymer resin. Emulsion, vinyl acetate-polyvinyl ercol copolymer resin emulsion, vinyl acetate-vinyl chloride copolymer resin emulsion, acrylic emulsion, acrylic silicone emulsion, styrene-acrylic copolymer resin emulsion, polystyrene emulsion, urethane emulsion, chlorinated polyolefin emulsion, epoxy- Examples include acrylic dispersion and SBR latex.
[0020]
The thickness of the ultraviolet absorbing layer is appropriately selected so that the reflectance from the ultraviolet absorbing layer is substantially 0 (zero). For example, when the ultraviolet absorber is emulsion tinuvin and the wavelength of the light source is 254 nm, the thickness of the ultraviolet absorbing layer is sufficient to be 1 μm or less, for example, in the range of 0.1 to 1 μm. When the wavelength of the light source is 350 nm, the thickness of the ultraviolet absorbing layer is suitably in the range of 3 to 5 μm, for example.
[0021]
The fluorescent printing material of the second aspect of the present invention comprises at least a substrate, an ultraviolet absorbing layer, and a protective layer that is substantially transparent to ultraviolet and visible light.
The base material is the same as that exemplified for the fluorescent printing material of the first aspect.
Further, the ultraviolet absorbing layer may be one in which the ultraviolet absorbent is not substantially fixed to the ultraviolet absorbing layer, other than those exemplified for the fluorescent printing material of the first aspect as it is. . For example, the ultraviolet absorbing layer can be made of a resin and an ultraviolet absorber.
[0022]
Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, acrylate-based, and salicylate-based ultraviolet absorbers. Furthermore, examples of the benzophenone ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,4-dihydroxybenzophenone, Resorcinol monobenzoate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 2-hydroxy-4-n-octylbenzophenone and the like can be mentioned.
[0023]
Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole (Tinuvin P, manufactured by Ciba Geigy), 2- (2′-hydroxy-3′-t-butyl). -5′-methylphenyl) -5-chlorobenzotriazole (Tinuvin 326, manufactured by Ciba Geigy), 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl)] phenyl] -2H-benzotriazole (Tinubin 234, manufactured by Ciba Geigy Corporation) and the like.
[0024]
Examples of the acrylate ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, ethyl-2-cyano-3,3-diphenyl acrylate, and the like.
Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, 4-t-butylphenyl salicylate, p-octylphenyl salicylate, and the like.
[0025]
Moreover, as resin which comprises a ultraviolet absorber, resin substantially transparent with respect to visible light can be used. As such a resin, the resin exemplified as the resin serving as the vehicle component constituting the ultraviolet absorbing layer in the first aspect can be used.
[0026]
  Protective layer,For the fluorescent dye in the fluorescent ink and the ultraviolet absorber in the ultraviolet absorbing layerImperviousAnd furtherOptically,Against UV and visible lightTransparentIf it is what is. Furthermore, the protective layer is made of a resin on which the fluorescent ink is placed, that is, a resin that dissolves in a solvent constituting the fluorescent dye ink, and the fluorescent layer or a resin containing the fluorescent dye is easily fixed in the protective layer resin. Is appropriate. As an example of such a resin, it is possible to use the thermoplastic resin exemplified as the resin that becomes the vehicle component constituting the ultraviolet absorbing layer in the first aspect and an emulsion thereof. It is appropriate to determine the thickness of the protective layer in view of the fact that transfer and mixing of the ultraviolet absorber and the fluorescent dye can be effectively prevented. For example, a range of 0.2 to 5 μm is appropriate.
[0027]
Next, the manufacturing method of the fluorescent printing material of this invention is demonstrated.
The fluorescent printing material of the first aspect of the present invention can be produced by forming an ultraviolet absorbing layer on a substrate by a spray coating method or an ink jet method.
The fluorescent printing material of the second aspect of the present invention can be produced by forming a protective layer on the ultraviolet absorbing layer on the substrate by a spray coating method or an ink jet method.
[0028]
The spray coating method is a method of forming a uniform thin film by discharging ink from a narrow-mouth nozzle by pump pressure. The film pressure can be adjusted by changing the ink viscosity, nozzle diameter, air or pump pressure, and substrate carry-out speed.
By using the spray coating method, an ultraviolet absorbing layer or a protective layer having a uniform and thin coating film can be formed.
[0029]
The ink jet method is a method of forming a dot pattern by ejecting ink from nozzles using the vibration pressure of a piezo element generated by a pulse signal.
By using the inkjet method, an ultraviolet absorbing layer or a protective layer having a uniform and thin coating film can be formed.
[0030]
Next, the manufacturing method of the fluorescent printed material of this invention is demonstrated.
The manufacturing method of the 1st aspect of this invention prints the ink containing fluorescent dye on the ultraviolet absorption layer of the fluorescent printing material of the said 1st aspect of the said invention.
Moreover, the manufacturing method of the 2nd aspect of this invention prints the ink containing fluorescent dye on the protective layer of the fluorescent printing material of the said 2nd aspect of this invention.
[0031]
In the above-mentioned “ink containing a fluorescent dye”, the fluorescent dye may be any dye that emits fluorescence when irradiated with excitation light, and may be colored or colorless. As colorless fluorescent dyes, EB-501 (Mitsui Toatsu Dye Co., Ltd., emission color: blue), EG-302 (Mitsui Toatsu Dye Co., emission color: yellow green), EG307 (Mitsui Toatsu Dye Co., Ltd.) , Luminescent color: green), ER-120 (manufactured by Mitsui Toatsu Dye Co., Ltd., luminescent color: red), ER-122 (manufactured by Mitsui Toatsu Dye Co., Ltd., luminescent color: red) and Ubitec OB called fluorescent whitening agent ( Ciba Geigy, Inc., emission color: blue) and the like.
[0032]
In addition, colored fluorescent dyes have the property of emitting light in the same color as coloring. Examples include basic dyes such as cationic brilliant flavin (yellow), cationic brilliant red (red), cationic brilliant pink (peach), and spirone. Examples thereof include yellow (yellow), spiron red (red), sot pink (peach) (manufactured by Hodogaya Chemical Co., Ltd.), basic yellow, rhodamine B and the like.
[0033]
Furthermore, a luminescent pigment can also be used as the fluorescent dye. A luminescent dye is a dye that absorbs light in the ultraviolet region and converts the wavelength into the visible region to emit light. Examples of such dyes can be mentioned.
[0034]
In the production method of the present invention (both the first and second aspects), the ink containing a fluorescent dye is preferably printed by an ink jet method.
In the inkjet method, an electric field is applied to a method of forming a dot pattern by ejecting ink from a nozzle using the vibration pressure of a piezo element generated by a pulse signal or a low-viscosity high-speed ink flow containing an electrolyte. There is a method of forming a dot pattern by separating minute droplets of ink.
By using the inkjet method, there is an advantage that high-speed printing is possible especially when printing a barcode.
[0035]
The inkjet ink containing a fluorescent dye can contain the fluorescent dye, vehicle, water and an aqueous organic solvent.
As the vehicle, for example, the resin exemplified as the resin that becomes the vehicle component constituting the ultraviolet absorbing layer in the first aspect can be used. The water should just be the purity more than ion-exchange water.
[0036]
The water-soluble organic solvent is used for the purpose of preventing ink drying and imparting penetrability. For example, polyhydric alcohols such as ethylene glycol, diethylene glycol, polyethylene glycol, and glycerin: N-alkylpyrrolidones: esters such as ethyl acetate and amyl acetate. Class: Lower alcohols such as methanol, ethanol, propanol, butanol: glycol ethers such as methanol, butanol, and ethylene oxide or propylene oxide adducts of phenol. These water-soluble organic solvents are not limited to the above solvent examples, and may be used singly or in plural as appropriate in consideration of the hygroscopicity, moisture retention, dye solubility and permeability, ink viscosity, freezing point, etc. of the solvent. Used in. The usage fee of these water-soluble organic solvents is preferably in the range of 0.1 to 70% by weight of the ink.
[0037]
In order to satisfy various conditions required for the system of the ink jet recording apparatus, additives conventionally known as ink components may be added as necessary. These additives include alcohol amines, ammonium salts as pH adjusters, metal hydroxides: organic salts as specific resistance adjusters, inorganic salts: antioxidants: preservatives: fungicides: sequestering agents And chelating agents.
[0038]
In addition to the above composition, water-soluble resins such as polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, styrene acrylic acid resin, and styrene maleic acid resin are used to such an extent that blockage of the nozzle part and change in the ink ejection direction do not occur. Can also be added.
[0039]
The fluorescent printed matter according to the first aspect of the present invention is a printed matter having a printed layer formed of an ink containing a fluorescent dye on the ultraviolet absorbing layer of the fluorescent printing material according to the first aspect. Explaining in accordance with FIG. 1, a printed matter having a printed layer 3 formed of an ink containing a fluorescent dye on an ultraviolet absorbing layer 2 on a substrate 1. However, although not shown, a printing layer such as letters and patterns may be provided between the substrate 1 and the ultraviolet absorption layer 2.
[0040]
Moreover, the fluorescent printed matter of the 2nd aspect of this invention provides the printing layer formed with the ink containing fluorescent dye on the protective layer of the fluorescent printing material of the said 2nd aspect. Referring to FIG. 2, the substrate 1 has an ultraviolet absorbing layer 2, a protective layer 4 that is substantially transparent to ultraviolet rays and visible light, and a printing layer 3 formed of an ink containing a fluorescent dye in this order. . However, although not shown, a printing layer such as letters and patterns may be provided between the substrate 1 and the ultraviolet absorbing layer 2.
[0041]
The printing layer formed with the ink containing the fluorescent dye is preferably an invisible pattern and an invisible information pattern. Here, the pattern includes a non-information pattern and an information pattern. Examples of non-information patterns include detection marks. Moreover, a code pattern can be mentioned as an information pattern. An example of the code pattern is a barcode, and the barcode may be a two-dimensional code in addition to the one-dimensional barcode. In particular, the present invention is effective for a two-dimensional code because a high resolution can be obtained.
[0042]
The detection mark is a mark provided for setting a paper feed timing of a transparent sheet that is not optically detected when an image is formed by a copying machine using an optical detection method. The shape of the detection mark and the position on the transparent sheet where the detection mark is provided are not particularly limited. For example, detection marks described in JP-A-58-106550, JP-A-58-105157, JP-A-59-7367 and JP-A-3-99878 can be mentioned.
[0043]
【The invention's effect】
According to the present invention, even when a fluorescent printing layer is formed using an ink containing a fluorescent dye, the material having an ultraviolet absorbing layer as a backcoat layer, the fluorescence intensity of the formed fluorescent printing layer is reduced. A fluorescent printing material that can be prevented can be provided.
Furthermore, according to the present invention, there is provided a printing method for forming a fluorescent printing layer using an ink containing a fluorescent dye on a material having an ultraviolet absorbing layer as a backcoat layer, wherein the fluorescence intensity of the formed fluorescent printing layer is reduced. It is possible to provide a method for producing a fluorescent printed matter capable of preventing the above.
[0044]
In addition, according to the present invention, the backcoat layer has a UV-absorbing layer and a fluorescent printing layer formed with an ink containing a fluorescent dye thereon, and the fluorescence intensity of the fluorescent printing layer maintains its original intensity. A fluorescent print can be provided.
Furthermore, according to the present invention, for example, a fluorescent printing layer such as a barcode can be formed at high speed by an inkjet printer, and information on the formed barcode can be taken out with high accuracy.
[0045]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
[0046]
Example 1
PET (polyethylene terephthalate film (thickness: 50 μm)) is used as a base material, and an ink having the following composition is used thereon, and an airless spray coating machine (Nordson Select Coat System) has a width of 2 cm and a length of 15 cm. Then, an ultraviolet absorbing layer having a thickness of 10 μm was formed to obtain the fluorescent printing material of the present invention. This ultraviolet absorbing layer absorbs almost 100% of light having a wavelength of 350 nm or less.
Ink composition for UV absorbing layer formation
30 parts by weight of resin-modified UV absorber (tinuvin emulsion)
70 parts by weight of pure water
[0047]
A fluorescent printing layer having a width of 2 cm, a length of 15 cm, and a thickness of 1 μm on the ultraviolet absorbing layer using an airless spray coating machine (Nordson Select Coat System) using an ink containing a fluorescent dye having the following composition. Formed.
Ink composition for fluorescent printing layer formation
Fluorescent dye (transparent brightener) Uvitex OB (Ciba Geigy) 1 part by weight
Polyester resin Byron 200 (Toray Industries, Inc.) 29 parts by weight
solvent
Methyl ethyl ketone (MEK) 35 parts by weight
35 parts by weight of toluene
A fluorescent dye was dissolved in MEK, and the resin and the remaining solvent were mixed to prepare.
[0048]
A control film in which only a fluorescent printing layer was formed on a substrate similar to the above without forming an ultraviolet absorbing layer was also produced.
Fluorescence emission of the film of the present invention in which the ultraviolet absorbing layer and the fluorescent printing layer were formed on the substrate obtained above and the control film in which only the fluorescent printing layer was formed on the substrate was measured. The measurement was performed using a mercury lamp having a dominant wavelength of 254 nm as a light source.
The results are shown in FIG. The film of the present invention had a fluorescence emission that was about 26% of the fluorescence emission of the control film.
[0049]
Example 2
As in Example 1, an ultraviolet absorbing layer was formed on the substrate. Next, a protective layer (width 2 cm, length 15 cm, thickness 0.5 μm) that is substantially transparent to ultraviolet light and visible light is formed on the ultraviolet absorbing layer using an ink having the following composition. It was formed with an airless spray coating machine (Nordson Select Coat System).
Ink composition for protective layer formation
30 parts by weight of vinyl acetate-vinyl chloride copolymer resin emulsion
70 parts by weight of pure water
[0050]
Next, a fluorescent printing layer was formed on the protective layer in the same manner as in Example 1 to obtain a film of the present invention.
Moreover, the control film which formed the protective layer and the fluorescence printing layer was also produced without providing an ultraviolet absorption layer on a base material.
The fluorescence emission of the obtained film of the present invention and the control film was measured in the same manner as in Example 1. The results are shown in FIG. The film of the present invention had a fluorescence emission that was about 66% of the fluorescence emission of the control film.
[0051]
Comparative Example 1
A UV-absorbing layer is formed on the substrate in the same manner as in Example 1 except that 1 part by weight of the resin-modified UV absorber (tinuvin emulsion) in the UV-absorbing layer is replaced with 0.5 part by weight of tinuvin. A fluorescent printing layer similar to that in Example 1 was formed thereon.
For the obtained film, the fluorescence emission intensity was measured in the same manner as in Example 1. However, virtually no luminescence was observed (the fluorescence emission intensity relative to the control film was 0%).
[0052]
Examples 3 and 4
A film was formed in the same manner as in Examples 1 and 2 except that the composition of the ultraviolet absorbing layer forming ink was changed as follows, the fluorescence emission intensity was measured, and the relative fluorescence emission intensity relative to the control film was calculated.
Ink composition for UV absorbing layer formation
Zinc oxide (ZnO) (average particle size 0.01 μm) 20 parts by weight
Polyester resin Byron 200 (Toray Industries, Inc.) 15 parts by weight
solvent
30 parts by weight of methyl ethyl ketone (MEK)
35 parts by weight of toluene
As a result, in Example 3 having no protective layer, the relative fluorescence emission intensity was about 25%, and in Example 4 having the protection layer, the relative fluorescence emission intensity was about 68%.
[0053]
Example 5
With respect to the film before forming the fluorescent printing layer obtained in Examples 1 to 4 (films having only an ultraviolet absorption layer: Examples 1 and 3, films having an ultraviolet absorption layer and a protective layer: 2 and 4) A barcode was formed with an ink jet printer (manufactured by Domino). The composition of the ink used was the same as that shown in Example 1.
The formed barcode was read by ultraviolet irradiation and tested. As a result, all bar codes could be read satisfactorily.
[0054]
Examples 6-8
For the purpose of confirming the ultraviolet absorbing effect of the fluorescent printing material having the ultraviolet absorbing layer on the substrate of the present invention, yellow paper and orange paper (red paper) (Example 6), blue paper and green paper (blue type) Paper) (Example 7) and gray paper (Example 8) were used to measure the diffuse reflectance in the ultraviolet region with and without the ultraviolet absorbing layer.
The ultraviolet absorbing layer forming ink used in Example 1 was applied on each paper to form a 1 μm ultraviolet absorbing layer, and the diffuse reflectance was measured. The results are shown in FIGS. In any case, in the ultraviolet region of 200 to 350 nm, the paper on which the ultraviolet absorbing layer is formed has a low reflectance (5% or less) equivalent to that of carbon black coated paper, and has an excellent ultraviolet absorbing effect. I understand.
[0055]
Example 9
For the purpose of confirming the ultraviolet absorption effect of a fluorescent printing material having an ultraviolet absorbing layer on the substrate of the present invention, using a fluorescent brightener-containing paper, the diffuse reflectance in the ultraviolet region, depending on the presence or absence of the ultraviolet absorbing layer Was measured.
The ultraviolet absorbing layer forming ink used in Example 1 was applied on the paper to form a 1 μm ultraviolet absorbing layer, and the diffuse reflectance was measured. The results are shown in FIG. In the optical brightener-containing paper that does not have an ultraviolet absorbing layer, it showed a diffuse reflectance of 200% or more at the maximum, whereas in the paper in which the ultraviolet absorbing layer was formed, in the ultraviolet region of 200 to 350 nm, It shows a low reflectance (less than 10%) that is close to that of carbon black-coated paper, indicating that it has an excellent ultraviolet absorption effect.
[0056]
Example 10
In the fluorescent printing material having the ultraviolet absorbing layer on the base material of the present invention, it was confirmed that the influence of the color change of the base material on the fluorescence emission intensity is smaller than that of the material without the ultraviolet absorbing layer. The following tests were conducted for the purpose of:
White (whitening agent included), white (no whitening agent included), blue, gray, green, brown, orange, yellow, and black papers were used as the base paper, and Example 6 was formed on each paper. A UV absorbing layer having a thickness of 1 μm was formed in the same manner as ˜8. In the same manner as in Example 1, a fluorescent printing layer having a thickness of 1 μm was formed on each of the paper on which the ultraviolet absorbing layer was formed and the paper on which the ultraviolet absorbing layer was not formed.
[0057]
For each of the obtained samples, the fluorescence intensity was measured in the same manner as in Example 1. The results are shown in FIG. For papers that do not have an ultraviolet absorbing layer, the light emission intensity obtained with black paper was about one-tenth of the light emission intensity obtained with white (whitening agent-containing) paper, whereas ultraviolet light absorption. In the fluorescent printing material of the present invention having a layer, the emission intensity obtained with black paper is about one-half that obtained with white (whitening agent-containing) paper, and the difference is greatly reduced. became.
This indicates that by using the fluorescent printing material of the present invention having an ultraviolet absorbing layer, the reading error of information on the fluorescent printing layer due to the difference in the underlying color of the fluorescent printing layer can be greatly reduced.
[Brief description of the drawings]
FIG. 1 is a cross-sectional explanatory view of a fluorescent printed material of the present invention.
FIG. 2 is a cross-sectional explanatory view of the fluorescent printed material of the present invention.
FIG. 3 is a fluorescence spectrum of the fluorescent print (film) of Example 1 and a control film.
4 is a fluorescence spectrum of the fluorescent print (film) of Example 2 and a control film. FIG.
5 shows measurement results of diffuse reflectance of paper (yellow, orange) having an ultraviolet absorbing layer (UV absorbing layer) and paper having an ultraviolet absorbing layer (yellow, orange) of Example 6. FIG.
6 shows measurement results of diffuse reflectance of paper (blue, green) having an ultraviolet absorption layer (UV absorption layer) and paper having an ultraviolet absorption layer (blue, green) of Example 7. FIG.
7 shows measurement results of diffuse reflectance of a sheet (gray) having an ultraviolet absorption layer (UV absorption layer) and a sheet (gray) having an ultraviolet absorption layer of Example 8. FIG.
8 shows measurement results of diffuse reflectance of a fluorescent brightener-containing paper having an ultraviolet absorbing layer (UV absorbing layer) and a fluorescent brightener-containing paper having an ultraviolet absorbing layer in Example 9. FIG.
9 is a measurement result of fluorescence luminance of each sheet of Example 10. FIG.

Claims (6)

A fluorescent printing material having a UV-absorbing layer on a base material and having a protective layer transparent to UV-light and visible light on the UV-absorbing layer; A method for producing a fluorescent print, wherein a printed layer is formed by printing ink,
The protective layer is a resin layer formed using an aqueous resin emulsion and is impermeable to the fluorescent dye in the ink and the ultraviolet absorber in the ultraviolet absorbing layer. Manufacturing method. The manufacturing method of Claim 1 which forms a protective layer on the ultraviolet absorption layer on a base material with a spray coat system or an inkjet system. The production method according to claim 1 or 2 , wherein printing of the ink containing the fluorescent dye is printing of a barcode by an ink jet method.  The substrate has an ultraviolet absorbing layer, a protective layer transparent to ultraviolet rays and visible light, and a printing layer formed with an ink containing a fluorescent dye in this order, and the protective layer is made of an aqueous resin emulsion. A fluorescent printed material, which is a formed resin layer and is impermeable to the fluorescent dye in the ink and the ultraviolet absorbent in the ultraviolet absorbing layer. The fluorescent printed material according to claim 4 , wherein the printed layer formed of an ink containing a fluorescent dye is a barcode. A method for reading a fluorescent barcode, comprising: reading the barcode of the fluorescent printed matter according to claim 5 using a light source having a wavelength in the range of 200 to 350 nm.

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